WO2011021258A1 - Procédé pour la préparation d'ester d'acide carbamique n-substitué et procédé pour la préparation d'isocyanate à l'aide de l'ester d'acide carbamique n-substitué - Google Patents

Procédé pour la préparation d'ester d'acide carbamique n-substitué et procédé pour la préparation d'isocyanate à l'aide de l'ester d'acide carbamique n-substitué Download PDF

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WO2011021258A1
WO2011021258A1 PCT/JP2009/005013 JP2009005013W WO2011021258A1 WO 2011021258 A1 WO2011021258 A1 WO 2011021258A1 JP 2009005013 W JP2009005013 W JP 2009005013W WO 2011021258 A1 WO2011021258 A1 WO 2011021258A1
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group
isomer
phenol
ring
aromatic
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PCT/JP2009/005013
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English (en)
Japanese (ja)
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三宅信寿
篠畑雅亮
大久保敦史
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旭化成ケミカルズ株式会社
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Priority to US13/001,238 priority Critical patent/US8884047B2/en
Priority to CN200980124092.1A priority patent/CN102105439B/zh
Priority to RU2010152832/04A priority patent/RU2528423C2/ru
Priority to CA2724634A priority patent/CA2724634C/fr
Priority to ES09845052.1T priority patent/ES2609025T3/es
Priority to KR1020107028732A priority patent/KR101332485B1/ko
Priority to JP2010539966A priority patent/JP5067906B2/ja
Priority to EP09845052.1A priority patent/EP2322504B9/fr
Priority to BRPI0919143-7A priority patent/BRPI0919143B1/pt
Publication of WO2011021258A1 publication Critical patent/WO2011021258A1/fr
Priority to US14/490,027 priority patent/US9249090B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/08—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/54—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/56—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/58—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a method for producing an N-substituted carbamic acid ester and a method for producing an isocyanate using the N-substituted carbamic acid ester.
  • Isocyanate is widely used as a raw material for producing polyurethane foam, paints, adhesives and the like.
  • the main industrial production method of isocyanate is assumed to have multiple reaction mechanisms, but is a reaction between an amine and phosgene as shown by the following formula (i) (phosgene method), which is almost the entire production volume of the world. Is produced by the phosgene method. However, the phosgene method has many problems.
  • the first is to use a large amount of phosgene as a raw material.
  • Phosgene is extremely toxic and requires special handling in order to prevent exposure to workers and special equipment to remove waste.
  • phosgene method a large amount of highly corrosive hydrogen chloride is by-produced, and thus a process for removing the hydrogen chloride is required.
  • isocyanate Hydrolyzable chlorine is contained, and when an isocyanate produced by the phosgene method is used, the weather resistance and heat resistance of the polyurethane product may be adversely affected.
  • a method for producing an isocyanate compound that does not use phosgene is desired.
  • a method for synthesizing an aliphatic isocyanate from an aliphatic nitro compound and carbon monoxide and a method for converting an aliphatic amide compound to isocyanate by Hofmann decomposition are known, but both methods are industrially poor in yield. This is an insufficient method for implementation.
  • An isocyanate and a hydroxyl compound can be obtained by thermal decomposition of an N-substituted carbamic acid-O-alkyl ester compound, for example, AWHoffmann (Non-patent Document 1, Berchte der Deutschen Chemischen Gesellshaft, Vol. 3, 653, 1870). This method has been known for a long time. This method can achieve a high yield relatively easily than the above method.
  • the basic reaction is illustrated by the following formula (ii).
  • the thermal decomposition reaction represented by the above general formula is reversible, and the equilibrium is biased toward the N-substituted carbamic acid-O-alkyl ester on the left side at low temperature, but the isocyanate and alcohol side on the right side is advantageous at high temperature. It becomes. Therefore, a method for obtaining isocyanate by thermal decomposition reaction of N-substituted carbamic acid-O-alkyl ester is performed under high temperature conditions (Patent Document 1, for example, US Pat. No. 7,122,697, Examples 12, 13 and the like).
  • the boiling point of the N-substituted carbamic acid-O-methyl ester is 110 ° C. (at a reduced pressure of about 2 kPa) (non-patent document) 2 (Journal of American Chemical Society, Volume 73, page 1831, 1951, 9th line from the top of the right column)
  • the boiling point of hexamethylene diisocyanate produced by the thermal decomposition reaction is 130 to 140 ° C (about 2 kPa reduced pressure) (Non-Patent Document 3, Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), pages 141 to 143, 19 That is, the N-substituted carbamic acid-O-methyl ester has a lower boiling point than the product hexamethylene diisocyanate.
  • thermal decomposition proceeds at 200 ° C. or higher, and when the thermal decomposition reaction is performed at 250 ° C. under the described reduced pressure, the conditions are such that the N-substituted carbamic acid-O -Since the temperature exceeds the boiling point of the methyl ester, a thermal decomposition reaction takes place in the gas phase.
  • the raw material N-substituted carbamic acid-O-methyl ester is also the product hexamethylene diisocyanate.
  • the by-product methanol is also mixed in the gas phase, and it is difficult to control the reaction, and it also causes various irreversible side reactions, including the above-mentioned H. Schiff sentence.
  • Non-Patent Document 4 Berchte der Deutschen Chemischen Gesellchaft, Vol. 3, 649, 1870
  • E. Dyer and GCWright's research Non-patent Document 5, Journal of American Chemical, vol.
  • N-substituted carbamic acid-O-alkyl esters can be converted to gas phase heat.
  • both the isocyanate concentration in the gas phase and the N-substituted carbamic acid-O-alkyl ester concentration are in a high state, so that an allophanate compound represented by the following formula (iii) is easily generated. Since the allophanate compound is produced by a crosslinking reaction, the boiling point of the allophanate compound is high, and the allophanate compound is liquefied in the reactor as soon as it is produced. Further, even in the liquefied state, the N-substituted carbamic acid-O-alkyl ester group is thermally decomposed, whereby the allophanate is easily cross-linked. Thus, it gradually solidifies, resulting in reactor blockage.
  • N-substituted carbamic acid-O-alkyl ester When N-substituted carbamic acid-O-alkyl ester is used as a raw material for the thermal decomposition reaction, not only does the yield and selectivity of the target isocyanate decrease due to these side reactions, but also polyisocyanate in particular. In the production of, the production of high molecular weight substances is caused, and in some cases, long-term operation such as clogging of the reactor due to precipitation of polymer solids is made difficult.
  • Patent Document 2 US Pat. No. 2,677,698
  • Patent Document 2 is a method for producing an aliphatic carbamic acid-O-alkyl ester without using phosgene.
  • N, N'-dialkylurea and hydroxy compound are reacted from aliphatic primary amine and urea to produce aliphatic carbamic acid-O-alkyl ester, and by-product primary amine is separated and recovered.
  • the method of returning to the first stage is described. This method is not satisfactory for industrial implementation because the process is extremely complicated because not only the yield of the produced carbamic acid ester is low but also a recycling facility for primary amine is required.
  • a bisurea is produced from an aliphatic primary polyamine, urea, and an alcohol, and then an N-substituted carbamic acid-O-alkyl ester is produced.
  • urea and alcohol are partially reacted in the first step, and in the subsequent second step, In this method, N-substituted carbamic acid-O-alkyl ester is produced by supplying diamine.
  • Patent Document 6 US Pat. No.
  • 4,497,963 is a method in which a primary amine and an N-unsubstituted carbamic acid-O-alkyl ester are mixed with an NH 2 group of the amine: carbamate: alcohol in the presence of the alcohol. N-substitution by reacting at a ratio of 1: 0.8 to 10: 0.25 to 50 at 160 ° C. to 300 ° C. in the presence or absence of catalyst and optionally removing the resulting ammonia. A carbamic acid-O-alkyl ester is obtained.
  • Patent Document 7 US Pat. No. 4,290,970
  • an aromatic diisocyanate and / or a polyisocyanate is produced through the following two steps.
  • an aromatic primary amine and an N-unsubstituted carbamic acid-O-alkyl ester are reacted in the presence or absence of a catalyst and in the presence or absence of urea and an alcohol, N-arylcarbamic acid-O-alkyl ester is obtained while removing by-product ammonia as necessary, and in the second step, the N-arylcarbamic acid-O-alkyl ester is subjected to a thermal decomposition reaction to give an aromatic Isocyanate is obtained.
  • Patent Document 8 Japanese Patent Laid-Open No.
  • N-alkylcarbamic acid-O-alkyl ester is produced after producing bisurea from aliphatic primary polyamine, urea and alcohol. It is a method to do.
  • the method described in Patent Document 9 (US Pat. No. 2,409,701) is a method for producing an aliphatic O-alkyl monourethane by reacting an aliphatic primary amine and urea with an aliphatic alcohol. .
  • the thermal decomposition reaction for producing an isocyanate from these N-substituted carbamic acid-O-alkyl esters requires a high temperature, and, for example, a high molecular weight product due to an undesirable side reaction as shown in the above formula (3). Cause the generation of. Most of the undesirable side reactions are likely to occur in the high temperature region.
  • the isocyanate produced by the thermal decomposition reaction is a reaction component such as the unreacted N-substituted carbamic acid-O-alkyl ester (the raw material for the thermal decomposition reaction is poly (N-substituted carbamic acid-O-alkyl ester)).
  • some of the carbamic acid esters include those having an isocyanate group, etc.), and the time of contact with a longer time tends to increase.
  • Various methods have been proposed in order to suppress the formation of undesired by-products generated during the thermal decomposition reaction of N-substituted carbamic acid-O-alkyl esters and to obtain a good isocyanate yield.
  • N-substituted carbamic acid-O-ester is a carbamic acid ester containing a carbamic acid group and an organic group.
  • the organic group is an aromatic hydroxy group.
  • N-substituted carbamic acid-O-aryl ester derived from a group and / or N-substituted carbamic acid-O-alkyl ester wherein the organic group is derived from an alcohol).
  • N-substituted carbamic acid-O-aryl ester in which the ester group constituting the ester is an aromatic group that is, a carbamic acid ester group derived from an aromatic hydroxy group
  • N-substituted carbamine in which the ester group is an alkyl group there is an advantage that the temperature of the thermal decomposition reaction can be set lower than that of acid-O-alkyl ester (for example, Patent Document 10: Pat. No. 3,992,430). That is, if the thermal decomposition temperature can be set low, the above-mentioned undesirable by-products can be suppressed.
  • the method for producing this N-substituted carbamic acid-O-aryl ester is more difficult than the method for producing N-substituted carbamic acid-O-alkyl ester.
  • the cause originates in the reactivity of alcohol used as the raw material of each esterification reaction, and an aromatic hydroxy compound.
  • the first reason is that the aromatic hydroxy compound is less nucleophilic than alcohol.
  • the second reason is that the esterification reaction is difficult to occur because the aromatic hydroxy compound is a weak acid.
  • Patent Document 11 US Pat. No. 4,297,501
  • a method is described in which N-substituted carbamic acid-O-aryl esters are oxidatively produced from primary amines, carbon monoxide and aliphatic alcohols or aromatic hydroxy compounds using noble metal catalysts.
  • this method has problems such as complicated operation and high cost. The problem is that due to the use of highly toxic carbon monoxide and the use of expensive noble metal catalysts, the catalyst must be recovered from the product N-substituted carbamic acid-O-aryl ester. .
  • Patent Document 12 US Pat. No. 3,873,553
  • an N-alkyl-N, N′-dialkylurea, an aromatic hydroxy compound, and hydrogen chloride gas are reacted to form an N-substituted carbamic acid-
  • This is a method for producing an O-aryl ester.
  • the problems are the use of corrosive hydrogen chloride gas, the consumption of expensive and special urea compounds, and the by-product N, N′-dialkylamine hydrochloride to N-substituted carbamate-O-aryl It is difficult to recover the ester.
  • Patent Document 13 US Pat. No.
  • Patent Document 15 Japanese Unexamined Patent Publication No. 2-759
  • Patent Document 16 Japanese Unexamined Patent Publication No. 3-20254 disclose urea and / or O-aryl carbamate (N-unsubstituted carbamic acid-O). -Aryl ester), and a method for producing an aliphatic O-aryl urethane from a one-step reaction of an aromatic hydroxy compound and an aliphatic primary amine.
  • Patent Document 17 Japanese Patent Laid-Open No. 8-277255
  • primary polyamine, urea and / or N-unsubstituted carbamic acid ester and organic hydroxy compound are continuously supplied to a reaction tower, and the corresponding urethane is supplied.
  • a method is disclosed in which urethane is produced continuously while ammonia generated in the reaction tower is continuously extracted from the reaction tower.
  • Patent Document 18 Japanese Patent Laid-Open No.
  • Patent Document 19 Japanese Patent Laid-Open No. 7-157463
  • an aliphatic primary polyamine, an aromatic hydroxy compound, urea and / N-unsubstituted carbamic acid-O-aryl ester are reacted.
  • N-substituted carbamic acid-O-aryl ester is recovered from the obtained reaction solution and recycled as a raw material for the reaction. is there. That is, the use amount of urea or N-unsubstituted carbamic acid-O-aryl ester is suppressed.
  • an N-unsubstituted carbamic acid-O-aryl ester contained in the reaction solution is thermally decomposed to obtain an aromatic hydroxy compound and isocyanic acid.
  • the aromatic hydroxy compound is distilled at a low temperature, the isocyanate
  • the acid is again reacted with the distilled aromatic hydroxy compound and recovered as an N-unsubstituted carbamic acid-O-aryl ester.
  • This method is complicated in operation, and the recovery rate of N-unsubstituted carbamic acid-O-aryl ester is not satisfactory.
  • Patent Document 22 discloses an N-substituted carbamine. It does not solve the problems in the production of acid-O-alkyl esters.
  • Patent Document 23 discloses a method for producing hexamethylene diisocyanate. In this method, hexamethylene dicarbamic acid-O-ethyl ester is thermally decomposed using dibenzyltoluene as a solvent in the presence of a catalyst mixture containing methyltoluenesulfonate and diphenyltin dichloride.
  • a catalyst mixture containing methyltoluenesulfonate and diphenyltin dichloride.
  • an alicyclic dicarbamic acid-O-alkyl ester is obtained by reacting an alicyclic primary diamine, urea and alcohol,
  • This is a circulation method for producing an alicyclic diisocyanate by thermally decomposing an alicyclic dicarbamic acid-O-alkyl ester.
  • This method is used by recovering unreacted alcohol, N-unsubstituted carbamic acid-O-ester, dialkyl carbonate and recycling a part of the reaction mixture and by-products of the pyrolysis step to the first step. It is intended to reduce raw materials.
  • this method requires distillation of the alicyclic dicarbamic acid-O-alkyl ester at a high temperature of about 230 ° C.
  • distillation temperature is a temperature range in which carbamic acid-O-alkyl ester is thermally decomposed
  • an isocyanate group generated during distillation reacts with the alicyclic dicarbamic acid-O-alkyl ester to form a solid multimer. Is a condition that can be generated.
  • the yield is maintained over a long operation time, but there is no description of the accumulation of multimers due to side reactions or the presence or absence of blockage of the apparatus.
  • Patent Document 26 Japanese Patent No. 3382289
  • Japanese Patent No. 3382289 is a method of partially removing worthless by-products before thermally decomposing N-substituted carbamic acid-O-alkyl ester. It is a method to increase the selectivity and the space-time yield during the pyrolysis reaction. However, this method also removes the N-substituted carbamic acid-O-alkyl ester together with a partially removed by-product, resulting in a decrease in the yield of isocyanate relative to the raw material primary amine and carboxylic acid derivative. .
  • a by-product that remains in the reactor without being discharged from the reactor is heated to form a polymer compound, and the compound adheres to the reactor. Is difficult.
  • urea or a carbonic acid derivative or a carboxylic acid derivative
  • a primary amine an alcohol or an aromatic hydroxy compound to obtain an N-substituted carbamic acid-O- (alkyl or aryl) ester
  • an expensive primary amine is used.
  • an excessive amount of urea, urea, or a carbonic acid derivative (or carboxylic acid derivative) is used.
  • the reaction formula of N-substituted carbamic acid-O-alkyl ester using primary amine and urea as raw materials is represented by the following formula (iv).
  • a sufficient amount of urea is present relative to the primary amine, but at the later stage of the reaction, the concentrations of both (primary amine and urea) decrease, and the N-substituted carbamic acid-O-alkyl ester is reduced. It will be present at high concentration.
  • the carbonyl carbon of urea and carbonic acid derivatives has low cationicity (because they receive electron donation from NH 2 group or alkoxy group), and the carbonyl of the N-substituted carbamic acid-O-alkyl ester that is the product.
  • the difference in reactivity between carbon and primary amine is small. Therefore, if the urea amount does not exist in a large excess relative to the primary amine, the reaction represented by the formula (v) proceeds in the later stage of the reaction.
  • the primary amine reacts with the product N-substituted carbamic acid-O- (alkyl or aryl) ester to modify it into a compound having an undesired N, N-disubstituted urea bond.
  • each amino group reacts sequentially, so that various modified products other than the following formula (v) are generated.
  • N-substituted carbamic acid-O- (alkyl or aryl) ester accumulates and urea concentration decreases, such as a reaction based on the formula (vii) that reacts with an isocyanate formed according to the formula (vi), these It can be easily estimated that the denaturation of the water greatly proceeds with knowledge of organic chemistry and reaction rate.
  • the high molecular weight product produced based on the above reaction has extremely low solubility in a solvent or the like, so that the high molecular weight product is often attached to the reactor, solidified, etc., and is not an industrially satisfactory method. .
  • bisurea is produced from a primary amine, urea, and alcohol, and the bisurea and alcohol are reacted to form an N-substituted carbamic acid-O-alkyl ester.
  • a production method (see Patent Document 4) has also been studied, but it is intended for reaction with a highly nucleophilic alcohol and is intended to thermally decompose the N-substituted carbamic acid-O-alkyl ester.
  • Patent Document 27 Japanese Patent No. 2804132
  • N-substituted carbamic acid-O- (alkyl or aryl) ester made from urea or N-unsubstituted carbamic acid-O-ester as a raw material can be used in any of the methods studied so far. It is difficult to obtain in high yield, and usually in the reaction product, a compound having a urea bond (-NHCONH-), a compound having a urea terminal (-NHCONH 2 ), an amino group terminal (-NH 2 ) In most cases, a compound having an allophane, a compound having an allophanate bond, and the like coexist.
  • N-substituted carbamic acid-O- (alkyl or aryl) esters using urea or carbonic acid derivatives. It is known that the corresponding isocyanates can be obtained by thermal decomposition of N-substituted carbamic acid-O- (alkyl or aryl) esters. However, when N-substituted carbamic acid-O-alkyl ester is used as a precursor, the thermal decomposition temperature is high, and the resulting isocyanate reacts with the N-substituted carbamic acid-O-alkyl ester as a raw material to modify. Is likely to occur.
  • the disclosed method requires the use of an excess of urea or carbonic acid derivative relative to the primary amine amino group in order to improve the yield of the relatively expensive primary amine standards.
  • a method for efficiently recovering and reusing excessively used urea or carbonic acid derivative and an increase in the basic unit of urea or carbonic acid derivative is inevitable.
  • the present inventors have disclosed a method for suppressing the thermal denaturation reaction of an N-substituted carbamic acid-O-alkyl ester using a specific aromatic hydroxy compound as a reaction solvent (International Patent Application Publication No. WO2008 / 120645).
  • a N-substituted carbamic acid-O-alkyl ester obtained by reacting a carbonate ester with a primary amine is thermally decomposed in the presence of an aromatic hydroxy compound, a small amount of a carbonic acid derivative is allowed to coexist.
  • a method for improving the thermal stability of an aromatic hydroxy compound International Patent Application Publication No. WO2008 / 084824 has been disclosed.
  • An object of the present invention is to provide a method for producing an N-substituted carbamic acid-O-aryl ester without various problems as described above, and production of an isocyanate by thermal decomposition of the N-substituted carbamic acid-O-aryl ester. It is to provide a method.
  • N-substituted carbamic acid-O-aryl ester is obtained, and the N-substituted carbamic acid-O-aryl ester is found to be solved by a method of thermally decomposing the N-substituted carbamic acid-O-aryl ester to produce an isocyanate. It was.
  • a carbamic acid-O-aryl ester is an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted by a number of ureido groups
  • a is an integer of 1 to 10
  • Ring A represents an organic group containing an integer number of carbon atoms in the range of 6 to 50, containing an aromatic group substituted with b hydroxy groups at any position that maintains aromaticity
  • the ring may be monocyclic, plural rings or heterocyclic, and may be substituted with other substituents
  • b is an integer of 1 to 6.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with c NH 2 groups, and c is an integer of 1 to 10.
  • the organic primary amine is an organic primary monoamine or an organic primary diamine.
  • the step (A) is carried out in the presence of water and / or an alcohol and / or an aromatic hydroxy composition containing at least one aromatic hydroxy compound.
  • R 2 group represents an aliphatic group having an integer carbon atom in the range of 1 to 14 or an aliphatic group to which an aromatic group is bonded
  • the OH group of the alcohol represented by the formula (4) is an aromatic ring. It is an OH group which is not bonded to.
  • the number of molecules of the aromatic hydroxy compound in the aromatic hydroxy composition containing at least one aromatic hydroxy compound represented by the following formula (2) is an integer of 1 to 100.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted by a number of ureido groups
  • a is an integer of 1 to 10
  • Ring A represents an organic group containing an integer number of carbon atoms in the range of 6 to 50, containing an aromatic group substituted with b hydroxy groups at any position that maintains aromaticity
  • the ring may be monocyclic, plural rings or heterocyclic, and may be substituted with other substituents, and b is an integer of 1 to 6.
  • I will provide a.
  • N-substituted carbamic acid-O-aryl ester (Where: R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with c NH 2 groups, c is an integer of 1 to 10, Ring A represents an organic group containing an integer number of carbon atoms in the range of 6 to 50, containing an aromatic group substituted with b hydroxy groups at any position that maintains aromaticity, The ring may be monocyclic, plural rings or heterocyclic, and may be substituted with other substituents, and b is an integer of 1 to 6. ).
  • the organic primary amine is an aromatic organic monoprimary amine represented by the following formula (5), and after the step (B) or after the step (R), or the step ( The following step (C) is performed after P), and the N-substituted carbamic acid-O— (R 2 or aryl) obtained in the step (B), the step (R), or the step (P) From the ester, at least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are bridged with the methylene group (—CH 2 —), N-substituted carbamic acid —O— (R 2 or aryl) )
  • At least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are obtained by crosslinking an aromatic group derived from an aromatic organic monoprimary amine contained in the ester with a methylene group (—CH 2 —).
  • N-substituted carbamic acid-O— (R 2 or aryl) ester represents N-substituted carbamic acid-O—R 2 ester or N-substituted carbamic acid-O-aryl ester.
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring a substituted to group at any position to keep the ring from R 3 may be substituted an aromatic ring each independently R 6 groups, also with an aromatic ring from R 3 by bonding R 6 originally between R 3 to R 6 groups may be hydrogen atoms or groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aryl groups having hydroxy groups, saturated aliphatic bonds and / or An aromatic group represented by the formula (5), which is a group selected from a group
  • the total number of carbon atoms constituting the organic mono primary amine is 6 to 1 It consists of an integer number of. )
  • the preceding item including a step of recovering urea by performing the following step (D) before and / or simultaneously with the step (B) or (P). 8] or [9]: Step (D): A step of removing urea by distillation or sublimation.
  • Step (E) A step of recycling the recovered urea to the step (A).
  • the N-substituted carbamic acid-O-aryl ester is thermally decomposed in the following step (F), and is represented by the following formula (6) derived from the N-substituted carbamic acid-O-aryl ester.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with s NCO groups, and s is an integer of 1 to 10.
  • Ring A is an aromatic ring selected from a benzene ring, a naphthalene ring, and an anthracene ring, and an OH group and R 7 to R 14 groups each represent a group that substitutes at any position that maintains the aromaticity of ring A; it from R 7 may be replaced with ring a each independently R 14 groups may form a ring together with the aromatic ring bonded from R 7 by bonding R 14 originally each other in the ring a, R 7 to R 14 groups are each independently a hydrogen atom, a halogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aryl group having a hydroxy group, an aralkyl group, an ether group (substit
  • a group a group selected from said group of above selected from groups consisting of group bonded through a saturated aliphatic bond and / or an ether bond, R 14 from a ring A and R 7, the total number of carbon atoms is 6
  • Consists of an integer number ranging from 50 to 50 b represents an integer of 1 to 6
  • d, e, f, g, h, i, j, k represents an integer of 0 to 5, and the value of d + e + f + g + h + i + j + k is the value when ring A is a benzene ring; 6 ⁇ b And when ring A is a naphthalene ring; when it is an integer of 8-b and when ring A is an anthracene ring; it represents an integer of 10-b, and is a group selected from R 7 to R 14 as described above May be bonded to ring A cyclically by a carbon-carbon bond and / or an ether bond.
  • a group a group selected from said group of above selected from groups consisting of group bonded through a saturated aliphatic bond and / or an ether bond, R 14 from a ring A and R 7, the total number of carbon atoms is 6
  • Consists of an integer number ranging from 50 to 50 b represents an integer of 1 to 6
  • d, e, f, g, h, i, j, k represents an integer of 0 to 5, and the value of d + e + f + g + h + i + j + k is the value when ring A is a benzene ring; 6 ⁇ b And when ring A is a naphthalene ring; when it is an integer of 8-b and when ring A is an anthracene ring; it represents an integer of 10-b, and is a group selected from R 7 to R 14 as described above May be bonded to ring A cyclically by a carbon-carbon bond and / or an ether bond.
  • Step (G) A step of collecting ammonia by-produced, reacting with carbon dioxide to regenerate urea, and recycling it to step (A).
  • an N-substituted carbamic acid-O-aryl ester of the present embodiment side reactions are suppressed by producing from a compound having a ureido group and an aromatic hydroxy composition, and the reaction is excessive.
  • an N-substituted carbamic acid-O-aryl ester can be produced without impairing the amount of urea and organic primary amine used.
  • various by-products can be suppressed and the various by-products can be dissolved and removed out of the system by the aromatic hydroxy composition, it is possible to operate for a long time.
  • the composition for transport and storage having a ureido group can be suitably used as a raw material for producing the N-substituted carbamic acid-O-aryl ester.
  • the conceptual diagram showing the manufacturing method of the compound which has a ureido group by the process (A) in this Embodiment is shown.
  • the conceptual diagram showing the process (B) in this Embodiment is shown.
  • the conceptual diagram showing the process (R) in this Embodiment is shown.
  • the conceptual diagram showing the process (P) in this Embodiment is shown.
  • the conceptual diagram showing the process (P) in this Embodiment is shown.
  • the conceptual diagram showing the process (P) in this Embodiment is shown.
  • the conceptual diagram showing the process (P) in this Embodiment is shown.
  • the conceptual diagram showing the manufacturing method of N-substituted carbamic acid ester which uses the aromatic hydroxy composition containing an active aromatic hydroxy compound and an inactive aromatic hydroxy compound in this Embodiment is shown.
  • the conceptual diagram which combined the route 1) which is one of this Embodiment, a process (D), a process (E), a process (F), and a process (G) is shown.
  • the conceptual diagram which combined the route 2) which is one of this Embodiment, a process (D), a process (E), a process (F), and a process (G) is shown.
  • the conceptual diagram which combined route 3) which is one of this Embodiment, a process (D), a process (E), a process (F), and a process (G) is shown.
  • the conceptual diagram which combined route 4) which is one of this Embodiment, a process (D), a process (E), a process (F), and a process (G) is shown.
  • the conceptual diagram which combined route 5) which is one of this Embodiment, a process (D), a process (E), a process (F), and a process (G) is shown.
  • the conceptual diagram showing the N-substituted carbamic-acid ester manufacturing apparatus in the Example of this Embodiment is shown.
  • the conceptual diagram showing the N-substituted carbamic-acid ester manufacturing apparatus in the Example of this Embodiment is shown.
  • 1 is a conceptual diagram showing an N-substituted carbamic acid monoester condensation apparatus in an example of the present embodiment.
  • the conceptual diagram showing the transesterification reaction apparatus in the Example of this Embodiment is shown.
  • the conceptual diagram showing the isocyanate manufacturing apparatus in the Example of this Embodiment is shown.
  • FIG. 2 is a conceptual diagram showing an N-substituted carbamic acid ester production apparatus in a comparative example of the present embodiment.
  • the conceptual diagram which shows the N-substituted carbamic-acid ester manufacturing apparatus in the Example of this Embodiment is shown.
  • the conceptual diagram which shows the urea manufacturing apparatus in the Example of this Embodiment is shown.
  • 1 shows the 1 H-NMR spectrum of a composition for transporting and storing a compound having a ureido group in Example 97 of the present embodiment.
  • 1 shows the 1 H-NMR spectrum of a composition for transporting and storing a compound having a ureido group in Example 106 of the present embodiment.
  • 1 shows the 1 H-NMR spectrum of a composition for transferring and storing a compound having a ureido group in Example 122 of the present embodiment.
  • 2 shows the 1 H-NMR spectrum of a composition for transporting and storing a compound having a ureido group in Example 142 of the present embodiment.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
  • composition for transferring and storing a compound having a ureido group in the present embodiment will be described.
  • composition ratio of the compounds contained in the composition for transporting and storing compounds having a ureido group will be described, and the detailed description of the compounds contained in the composition for transporting and storing compounds having a ureido group Will be done later.
  • the composition for transporting and storing a compound having a ureido group in the present embodiment is a composition for transporting and storing a compound having a ureido group, and the following formula (1) in the composition:
  • the aromatic hydroxy composition composition containing at least one aromatic hydroxy compound represented by the following formula (2)
  • the composition for transporting and storing a compound having a ureido group in which the number of molecules of the aromatic hydroxy compound is an integer of 1 or more and 100 or less.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted by a number of ureido groups
  • a is an integer of 1 to 10
  • Ring A represents an organic group containing an integer number of carbon atoms in the range of 6 to 50, containing an aromatic group substituted with b hydroxy groups at any position that maintains aromaticity
  • the ring may be monocyclic, plural rings or heterocyclic, and may be substituted with other substituents, and b is an integer of 1 to 6.
  • the compound having a ureido group used in this embodiment often has a high melting point because a hydrogen bond is easily formed between molecules by the ureido group constituting the compound having a ureido group.
  • a compound having a shaping process such as pulverization or processing into a pellet form of a solid ureido group, or a ureido
  • the compound having the ureido group is transferred as a liquid by heating to a temperature higher than the melting point of the compound having the group.
  • the compound having a certain amount of ureido group when the transfer line is blocked or the shape of the compound having a ureido group varies widely In many cases, a complicated apparatus is required to stably transfer the compound, and a step of aligning the shape of the compound having the ureido group within a certain range is required.
  • the temperature is higher than the melting point of the compound having a ureido group (for example, 150 ° C.) in consideration of preventing solidification during transfer.
  • the composition of this embodiment can suppress the heat denaturation reaction of the compound having a ureido group in the composition and stably hold the compound having a ureido group when the composition is transferred or stored. There is an effect.
  • the present inventors have found that the aromatic hydroxy compound constituting the composition has a ureido group. Since the ureido bond (—NHCONH 2 ) of the compound and the aromatic hydroxy compound having weak acidity form a hydrogen bond, a urethane bond is difficult to be close to each other, so that it has a ureylene group (—NHCONH—). It is presumed that reactions that form compounds and the like are unlikely to occur. Note that in the description of this embodiment, a ureylene group (—NHCONH—) may be referred to as a ureine group.
  • the composition for transfer and storage can be suitably used particularly in the production of N-substituted carbamic acid-O-aryl esters (hereinafter, N-substituted carbamic acid-O-aryl esters are frequently used).
  • the N-substituted carbamic acid-O-aryl ester represents an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring.
  • the composition for transfer and storage is transferred to an N-substituted carbamic acid-O-aryl ester synthesis step, and the compound having a ureido group contained in the composition is subjected to an esterification reaction.
  • the N-substituted carbamic acid-O-aryl ester produced is recovered.
  • the N-substituted carbamic acid-O-aryl ester synthesis step is at a high temperature, and is thermally stable if the compounds having the ureido group are supplied in a state having hydrogen bonds between molecules.
  • Modification to a compound having a ureylene group is thermodynamically advantageous.
  • the compound having the ureylene group is a condensate of the compound having the ureido group, and is a high molecular weight compound. Therefore, it often causes a problem of generating a high molecular weight substance and adhering to the reactor or solidifying.
  • the compound having a ureido group often contains a compound such as ammonia or urea.
  • These compounds, particularly urea, are often thermally decomposed into isocyanic acid and ammonia in the synthesis temperature range of the N-substituted carbamic acid-O-aryl ester synthesis step, and the isocyanate and the compound having the ureido group are Upon reaction, it is also modified into a compound having a biuret bond.
  • the thermal decomposition temperature of the compound having a biuret bond is high, and it is difficult to react with an aromatic hydroxy compound to produce an N-substituted carbamic acid-O-aryl ester.
  • the present inventors have disclosed a compound having a ureido group in transferring and storing the composition for transporting and storing, even when the composition for transporting and storing contains a specific amount of these ammonia and urea. It was found that the denaturation reaction was suppressed. The effect is particularly remarkable for long-term storage, and there are many cases that cannot be confirmed by accelerated evaluation. Such findings are surprising and unknown to date. Although the mechanism for expressing such an effect is not clear, the present inventors have found that the aromatic hydroxy compound is a compound such as ammonia or urea or a trace amount when the composition is transported and stored.
  • N-substituted carbamic acid-O-aryl ester is produced using the composition by trapping water and oxygen mixed in the mixture to suppress the modification reaction of the compound having a ureido group, It is speculated that it may also serve as an esterification catalyst for N-substituted carbamic acid-O-aryl esters.
  • the number of ureido groups constituting the compound having a ureido group having the number of molecules (y) of the aromatic hydroxy compound constituting the aromatic hydroxy composition.
  • the ratio to the number (x) is in the range of 1 to 100.
  • y is preferably a large excess with respect to x.
  • the ratio of y to x is preferably in the range greater than 2 and less than 50, more preferably in the range greater than 3 and less than 20.
  • the compound having a ureido group contained in the composition contains an organic primary amine, urea and / or a carbonic acid derivative (described in detail later) and / or isocyanic acid. And / or a compound having a ureido group obtained by reacting with N-unsubstituted carbamic acid.
  • a compound having a ureido group obtained by reacting an organic primary amine with urea is more preferable.
  • the composition for transfer and storage may contain components other than the compound having an ureido group and the aromatic hydroxy compound.
  • Such components include the above-mentioned ammonia, urea, carbonic acid derivatives (the carbonic acid derivatives shown in this embodiment will be described in detail later), N-unsubstituted carbamic acid, compounds having a biuret bond, and ureylene groups.
  • N-substituted carbamic acid-O-ester such as N-substituted carbamic acid-O- (alkyl or aryl) ester obtained by reaction.
  • the composition for transport and storage contains a compound containing a nitrogen atom, and the aromatic hydroxy compound is often oxidized and denatured by oxygen, and a decrease in coloring or the like is often observed. Moreover, since the said composition becomes a flammable composition in most cases, you may manage oxygen gas by a well-known method similarly to storage and storage of the normal organic chemical substance performed in the said technical field.
  • the gas phase oxygen concentration in the storage tank is controlled to be, for example, 10% or less, preferably 1% or less, more preferably 100 ppm or less by a method such as nitrogen purge.
  • an inert gas such as nitrogen
  • the oxygen concentration in the inert gas is controlled to 10 ppm or less.
  • Ammonia does not have a significant adverse effect, but the dissolved ammonia concentration in the composition is controlled to 1 wt% or less, preferably 0.1% or less.
  • the management method may be performed by a known method such as purging an inert gas such as nitrogen in the liquid phase.
  • the water concentration is high, the composition may cause a non-uniform decrease. Therefore, depending on the composition of the composition, the water concentration is 10% wt or less, preferably 1 wt% or less in the composition.
  • the composition is used as a raw material for an N-substituted carbamic acid-O-aryl ester, side reactions derived from water may occur when a large amount of water is present, and therefore, the composition is more preferably controlled to 100 ppm or less.
  • the water management method is carried out by a known method such as using a dehydrating agent, a desiccant, distilling under reduced pressure, increased pressure, or atmospheric pressure, or purging an inert gas into the liquid phase and taking it out with water.
  • a dehydrating agent such as organic acid and inorganic acid
  • a desiccant distilling under reduced pressure, increased pressure, or atmospheric pressure
  • an oxidizing substance or a reducing substance is present, the aromatic hydroxy compound may be denatured. Therefore, these substances are managed by a known method for managing an aromatic hydroxy compound.
  • the oxidizing substance refers to Bronsted acid and Lewis acid such as organic acid and inorganic acid
  • the reducing substance refers to Bronsted base such as organic base and inorganic base, Lewis base and hydrogen gas.
  • the reducing substance excludes compounds derived from the composition such as ammonia, urea, carbonic acid derivatives, and compounds constituting the composition (for example, N-substituted carbamic acid-O-aryl esters, N-substituted compounds).
  • N-substituted carbamic acid-O such as carbamic acid-O-alkyl ester, N-substituted carbamic acid-O-R 2 ester (the N-substituted carbamic acid-O-R 2 ester will be described in detail later) -Esters).
  • N-substituted carbamic acid-O- () obtained in the step of producing an N-substituted carbamic acid-O-aryl ester from the transporting and storing composition and an aromatic hydroxy composition (described in detail later)
  • the content of the R 2 or aryl) ester (the N-substituted carbamic acid-O—R 2 ester will be described in detail later) is not particularly limited, but the compound having the ureido group during storage and the N A composition for transport and storage since it may be condensed with a substituted carbamic acid-O- (R 2 or aryl) ester to form a ureylene group by reacting with a dealcohol or dearomatic hydroxy compound.
  • the amount of the compound having a ureido group contained in the product is controlled to 10 mol equivalent or less, preferably 1 mol equivalent or less.
  • Other components that may be included include urea and alcohol.
  • the transfer and storage compositions may be in a slurry state or in a solid state. It is preferably in a slurry state, more preferably in a liquid state. Since urea tends to solidify, in consideration of fluidity, it is 20 mol equivalent or less, preferably 10 mol equivalent, relative to the compound having a ureido group contained in the composition for transport and storage. Manage as follows. Although there is no restriction
  • the compound having a ureido group contained in the composition for transfer and storage it is controlled to 100 mol equivalent or less, preferably 10 mol equivalent or less.
  • the notation of N-substituted carbamic acid-O- (R 2 or aryl) ester is often used, but “N-substituted carbamic acid-O—R 2 ester or N-substituted carbamic acid-O-aryl” is used.
  • the conditions for storing and transporting the composition are not particularly limited, but there are cases where the thermal decomposition reaction of the compound having the ureido group is very likely to occur at high temperatures. Although it depends on the storage period, it is preferably in the range of minus 40 ° C. or more and 280 ° C. or less at the time of storage. However, it may be managed in accordance with the intended use and storage period of the composition and the handleability of the composition. Although the temperature at the time of transfer is also within the temperature range at the time of storage, the composition is used as a raw material for the N-substituted carbamic acid-O-aryl ester, and the N-substituted carbamic acid-O-aryl ester synthesis step is performed.
  • the composition When transferring, it is generally preheated to the reaction temperature and transferred to the reactor of the synthesis process. Therefore, transfer should be carried out after confirming that the transfer can be safely performed according to the conditions of the reaction process and the equipment of the reaction process. It doesn't matter. Usually, when the fluidity and stability are impaired in the range of minus 40 ° C. to 280 ° C., preferably 0 ° C. or more and 260 ° C. or less, more preferably 40 ° C. or more and 260 ° C. or less. As described above, the composition may be managed according to the intended use, transfer time, and handleability of the composition.
  • the pressure at the time of transfer is not particularly limited, but may be stored under reduced pressure to increased pressure.
  • the aromatic hydroxy composition When storing under reduced pressure, the aromatic hydroxy composition may be distilled off, so the ratio of the compound having a ureido group and the aromatic hydroxy compound in the composition is controlled to be in the above-mentioned range.
  • the storage container or piping when storing and transporting. Considering the flammable organic matter and taking into account the flash point of the composition to be handled, select a container in accordance with the laws and regulations of the region to be handled. There is no restriction
  • the storage tank and transfer equipment for the composition may be accompanied by other known equipment such as other pumps, temperature control equipment, and instrumentation equipment as necessary.
  • the composition for transporting and storing a compound having a ureido group described above includes a compound having a ureido group, an aromatic hydroxy composition, ammonia, and N-substituted carbamic acid-O— (R 2 or aryl).
  • Esters may be prepared by mixing urea, alcohol, carbonic acid derivatives and other components as described above so as to have the above-described composition, or have ureido groups obtained in the production of compounds having ureido groups.
  • an aromatic hydroxy composition, urea, alcohol, ammonia, a carbonic acid derivative, or the like may be added and / or removed so as to have the above-described composition.
  • the method shown later can be preferably carried out.
  • the present embodiment refers to an ester composed of a compound having a ureido group represented by the formula (1) and an aromatic hydroxy composition containing at least one aromatic hydroxy compound represented by the formula (2).
  • a compound having the ureido group and at least one N-substituted carbamic acid-O-aryl ester (where N -Substituted carbamic acid-O-aryl ester is a method for producing an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring.
  • the production method of the present embodiment includes a compound having a ureido group and an aromatic hydroxy composition (showing an aromatic hydroxy compound group containing at least one aromatic hydroxy compound) (described in detail later).
  • N-substituted carbamic acid-O-aryl ester and by-product ammonia by esterifying the compound having the ureido group and the aromatic hydroxy composition, or a compound having the ureido group
  • Esterification reaction with alcohol alcohol described later, alcohol represented as R 2 OH in formula (4) shown below
  • R 2 OH alcohol represented as R 2 OH in formula (4) shown below
  • N-substituted carbamic acid-O—R 2 ester and aromatic hydroxy composition are transesterified to produce N-substituted carbamic acid
  • the method for obtaining —O-aryl ester and by-produced alcohol (R 2 OH) is also this embodiment.
  • N-substituted carbamic acid derived from compound having ureido group and aromatic hydroxy composition— A method for producing O-aryl esters.
  • it is a method for producing an N-substituted carbamic acid-O-aryl ester from a compound having a ureido group and an aromatic hydroxy composition in a step including an esterification reaction. More specifically, it is a method for producing an N-substituted carbamic acid-O-aryl ester in an esterification reaction or a process including an esterification reaction and a transesterification reaction.
  • the esterification reaction refers to a reaction in which ammonia is by-produced by converting a ureido group (—NHCONH 2 ) in a compound having a ureido group into a carbamic acid ester group.
  • the ureido group is obtained as a carbamic acid-O-aryl ester group (—NHCOOAr)
  • a reaction that produces ammonia as a by-product of the reaction or a ureido group (—NHCONH 2 ) and an alcohol (R 2 OH) in a compound having a ureido group the ureido group is converted to a carbamic acid —O—R 2 ester group -NHCOOR 2 ) to produce ammonia as a by-product of the reaction.
  • Ar represented by the above carbamic acid-O-aryl ester group represents a residue obtained by removing one hydrogen atom of a hydroxyl group directly bonded to an aromatic hydrocarbon ring from an aromatic hydroxy compound. Further, the esterification reaction will be specifically described. From the compound having a ureido group represented by the formula (1) shown later and the aromatic hydroxy compound represented by the formula (2), the esterification reaction is represented by the formula (43).
  • N-substituted carbamic acid-O-aryl ester is obtained, and from a reaction that produces ammonia as a by-product, a compound having a ureido group represented by formula (1), and an alcohol represented by formula (4), the formula (4) resulting represented by N- substituted carbamic acid -O-R 2 ester in 49), pointing to the reaction by-produced ammonia.
  • the transesterification described above specifically refers to reacting an N-substituted carbamic acid-O—R 2 ester represented by the formula (49) with an aromatic hydroxy compound, and then reacting the N-substituted carbamine.
  • an esterification reaction is performed between a compound having a ureido group and an alcohol, and then an ester exchange reaction with an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound) is performed.
  • an aromatic hydroxy composition a composition containing at least one aromatic hydroxy compound
  • the method for producing the compound having a ureido group is a known method, for example, an organic primary amine, urea and / or a carbonic acid derivative (described in detail later) and / or isocyanic acid and / or N—
  • a compound having at least one ureido group which can be obtained by reacting an unsubstituted carbamic acid, preferably derived from the organic primary amine and urea by reacting the organic primary amine with urea.
  • the manufacturing method which obtains is preferable.
  • Organic primary amines preferably used in the present embodiment (the organic primary amine here is a description of Nomenclature of IUPAC Nomenclature of Organics defined by IUPAC (The International Union of Pure and Applied Chemistry)).
  • Primary amine (referring to mono primary amine and poly primary amine) defined in C-8 is an organic primary amine represented by the following formula (3). The rules are based on Recommendations on Organic & Biochemical Nomenclature. In the following, when referring to the IUPAC rules in this specification and the Nomenclature rules defined in the IUPAC (hereinafter, except for quoting IUPAC recommendations, etc. of other years), it is based on Recommendations 1979.
  • organometallic compounds and metal complexes include organometallic compounds and metal complexes.
  • organic and / or “organic group” and / or “substituent” and the like, and the compounds used in the present embodiment will be described below. And / or composed of atoms not containing metalloids. More preferably, H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom)
  • An aliphatic compound is a definition of a group in line with an aliphatic compound based on the 1995 IUPAC recommendation.
  • the recommendation defines an aliphatic compound as “Acyclic or cyclic, saturated or unsaturated carbon compounds, and excluded aromatic compounds”.
  • the aliphatic group often used in the present specification is a group composed of the aliphatic compound.
  • the group is defined as a monovalent aliphatic group, for example, an R moiety obtained by removing a hydrogen atom from an aliphatic compound called RH.
  • the aliphatic and aliphatic groups used in the description of the present invention contain both saturated and unsaturated, chain and cyclic, and the above-described H (hydrogen atom); C (carbon atom); N (nitrogen atom) O (oxygen atom); S (sulfur atom); Si (silicon atom); composed of an atom selected from halogen atoms selected from Cl (chlorine atom), Br (bromine atom) and I (iodine atom) “Organic compound”, “organic group” and “substituent”.
  • an aromatic group such as an aralkyl group
  • the “aliphatic group substituted with an aromatic group” or “group consisting of an aliphatic group bonded with an aromatic group” "Often written. This is based on the reactivity in the present embodiment, and the nature of the reaction of a group such as an aralkyl group is very similar to the reactivity of aliphatic rather than aromatic.
  • non-aromatic reactive groups including aralkyl groups, alkyl groups, and the like are often referred to as “aliphatic groups that may be aromatically substituted”, “aromatic substituted aliphatic groups”, and “aliphatic groups to which aromatic groups are bonded. "Etc.
  • the primary amine refers to an aliphatic compound and / or an aromatic compound having an amino group (—NH 2 ) residue and / or a compound in which an aliphatic group and an aromatic group are bonded. That is, the organic primary amine shown in the present application indicates “primary amine” classified as “organic” as described above.
  • the organic primary amine preferably used in the present embodiment is an organic primary amine represented by the following formula (3).
  • R 1 is an organic group containing a carbon atom in the range of 1 to 85, and represents an organic group substituted with c NH 2 groups, and c is an integer of 1 to 10.
  • R 1 is an organic group classified as “organic” as described above, and the organic primary amine in the present embodiment is an organic group having 1 to 85 carbon atoms and containing a carbon atom.
  • R 1 is an aliphatic group, an aromatic group, and aliphatic groups and aromatic groups are bonded group, acyclic hydrocarbon radical, cyclic hydrocarbon group (e.g., a monocyclic hydrocarbon group , condensed polycyclic hydrocarbon group, crosslinked cyclic hydrocarbon group, spiro hydrocarbon group, ring-assembly hydrocarbon group, a side chain cyclic hydrocarbon group, a heterocyclic group, heterocyclic spiro group, a hetero bridged ring group, group consisting of heterocyclic group), wherein the acyclic hydrocarbon group and the cyclic hydrocarbon group bonded one or more from the group selected from group and the group, has a specific non-metal atom (carbon, oxygen , Nitrogen, sulfur, silicon) and a group bonded through a covalent bond. Further, the specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon,) and covalent bond with the a, for example, the following formula (8) covalent bonds groups
  • the R 1 group that can be preferably used in the present embodiment includes an aliphatic group, an aromatic group, and an aliphatic group and an aromatic group, considering the difficulty of side reactions.
  • a group containing a carbon atom in the range of 1 to 85 In consideration of fluidity and the like, the group preferably contains a carbon atom in the range of 1 to 70. A group containing a carbon atom in the range of 1 to 13 is more preferable.
  • Preferred examples of the organic primary amine composed of the R 1 group include: 1) the R 1 group has 6 to 85 carbon atoms containing at least one aromatic ring which may be aliphatic and / or aromatically substituted.
  • An aromatic organic monoprimary amine which may be aliphatic and / or aromatically substituted, wherein the aromatic group in R 1 group is substituted by NH 2 group and c is 1 1 group is a group having 6 to 85 carbon atoms containing at least one aromatic ring which may be aliphatic and / or aromatically substituted, and the aromatic group in R 1 group is substituted by NH2 group, and c
  • an atom (preferably a carbon atom) to which the NH 2 group is bonded is expressed as an aromatic organic amine that is contained in an aromatic ring, and bonded to an atom (mainly carbon) that is not an aromatic ring.
  • the case where it exists is described as an aliphatic organic amine.
  • the more preferable aliphatic group has 6 to 70 carbon atoms, and includes a chain hydrocarbon group, a cyclic hydrocarbon group, and at least one group selected from the chain hydrocarbon group and the cyclic hydrocarbon group.
  • a bonded group for example, a cyclic hydrocarbon group substituted with a chain hydrocarbon group, a chain hydrocarbon group substituted with a cyclic hydrocarbon group, or the like).
  • aromatic organic mono primary amine R 1 group is a group having a carbon number of 6 to 85 containing one or more aliphatic and / or aromatic which may be substituted aromatic ring, in the R 1 group
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring
  • a group to be substituted at any position that keeps R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with the aromatic ring.
  • R 3 to R 6 groups Is a group composed of a hydrogen atom or a group in which a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and an aryl group having a hydroxy group is bonded by a saturated aliphatic bond and / or an ether bond
  • R 3 to R 6 groups have an integer of 0 to 7 carbon atoms, and the total number of carbon atoms constituting the aromatic organic monoprimary amine represented by formula (5) is an integer of 6 to 13 It is composed of pieces.
  • R 3 to R 6 groups are hydrogen atoms or groups selected from alkyl groups such as methyl groups and ethyl groups.
  • aromatic organic mono-primary amines include aniline, aminotoluene (each isomer), dimethylaniline (each isomer), diethylaniline (each isomer), dipropylaniline (each isomer) ), Aminonaphthalene (each isomer), aminomethylnaphthalene (each isomer), dimethylnaphthylamine (each isomer), trimethylnaphthylamine (each isomer), and the like.
  • aniline is more preferably used.
  • the aromatic organic polyprimary amine R 1 group is a group having 6 to 85 carbon atoms and containing at least one aromatic ring which may be aliphatic and / or aromatically substituted, and the aromatic in the R 1 group
  • R 1 group contains one or more aromatic rings, and the aromatic ring is further substituted with an alkyl group, an aryl group or an aralkyl group.
  • Examples include diaminobenzene (each isomer), diaminotoluene (each ecology), methylene dianiline (each isomer), diaminomesitylene (each isomer), diaminobiphenyl (each isomer), diaminodibenzyl.
  • each isomer bis (aminophenyl) methane (each isomer), bis (aminophenyl) propane (each isomer), bis (aminophenyl) ether (each isomer), bis (aminophenoxyethane) (each Isomers), ⁇ , ⁇ '-diaminoxylene (each isomer), diaminoanisole (each isomer), diaminophenetol (each isomer), diaminonaphthalene (each isomer), di (aminomethyl) benzene (each Isomer), di (aminomethyl) pyridine (each isomer), diaminomethylnaphthalene (each isomer), poly represented by the following formula (17) It can be exemplified Ji Ren polyphenyl polyamines.
  • Aliphatic organic polyprimary amine R 1 group of the organic primary amine represented by the formula (3) is an integer of an aliphatic group having 1 to 85 carbon atoms, which may be aromatically substituted.
  • c is an aliphatic organic polyprimary amine having 2 or 3.
  • the aliphatic group is a chain hydrocarbon group, a cyclic hydrocarbon group, or at least one group selected from the chain hydrocarbon group and the cyclic hydrocarbon group.
  • the R 1 group is an aliphatic group selected from an acyclic hydrocarbon group having 1 to 70 carbon atoms, a cyclic hydrocarbon group, and the acyclic hydrocarbon group and the cyclic hydrocarbon group.
  • a group to which at least one group is bonded for example, a cyclic hydrocarbon group substituted with an acyclic hydrocarbon group, an acyclic hydrocarbon group substituted with a cyclic hydrocarbon group, etc.).
  • c is an aliphatic organic polyprimary amine having 2 or 3.
  • the R 1 group is an acyclic hydrocarbon group having 6 to 13 carbon atoms composed of a carbon atom and a hydrogen atom, or cyclic carbonization.
  • a hydrogen group, and a group in which at least one group selected from the acyclic hydrocarbon group and the cyclic hydrocarbon group is bonded for example, a cyclic hydrocarbon group substituted with an acyclic hydrocarbon group, a ring An acyclic hydrocarbon group substituted with a formula hydrocarbon group).
  • the R 1 group is a linear and / or branched alkyl group, a cycloalkyl group, and a group composed of the alkyl group and the cycloalkyl group.
  • examples include ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopentane (each isomer), diaminohexane (each isomer), diaminoheptane (each isomer), diaminooctane ( Each isomer), diaminononane (each isomer), alkyl-diprimary amines such as diaminodecane (each isomer); triminohexane (each isomer), triaminoheptane (each isomer), triaminooctane (Each isomer), triaminononane (each isomer), alkyl-tri primary
  • the organic primary amines described in the above 1), 2) and 3) are preferably used.
  • the organic primary amine is an organic primary monoamine, an organic primary diamine or an organic primary triamine (the above formula (3) And c is more preferably 1 or an integer of 2 or 3.
  • a ureido group used for producing an N-substituted carbamic acid-O-aryl ester from the composition for transporting and storing a compound having a ureido group and / or an aromatic hydroxy composition of the present embodiment The compound which has is a compound represented by following formula (1).
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with a number of ureido groups, and a is an integer of 1 to 10.
  • the compound having a ureido group represented by the above formula (1) is a compound having a “ureido group” defined by Nomenclature rule C-971 defined by IUPAC.
  • R 1 is an organic group classified as “organic” as described above, and the compound having a ureido group in this embodiment includes a carbon atom in the range of 1 to 85 carbon atoms.
  • This is a compound having a ureido group in which a ureido group (—NH—CONH 2 ) is bonded to an organic group.
  • R 1 represents an aliphatic group, an aromatic group, a group formed by bonding an aliphatic group and an aromatic group, and is a non-cyclic hydrocarbon group, a cyclic hydrocarbon group (for example, a monocyclic hydrocarbon group, Fused polycyclic hydrocarbon group, bridged cyclic hydrocarbon group, spiro hydrocarbon group, ring assembly hydrocarbon group, cyclic hydrocarbon group with side chain, heterocyclic group, heterocyclic spiro group, hetero bridged ring group , A heterocyclic group), a group bonded with one or more groups selected from the acyclic hydrocarbon group and the cyclic hydrocarbon group, and the group is a specific nonmetal atom (carbon, oxygen, Represents a group bonded through a covalent bond to nitrogen, sulfur, or silicon. Further, the specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon,) and covalent bond with the a, for example, the following formula (8) covalent bonds groups groups and the represented by -
  • the R 1 group that can be preferably used in the present embodiment is selected from an aliphatic group and an aromatic group in view of the difficulty of side reactions, and is an acyclic hydrocarbon group.
  • Cyclic hydrocarbon group (monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, bridged cyclic hydrocarbon group, spiro hydrocarbon group, ring assembly hydrocarbon group, cyclic hydrocarbon group with side chain)
  • the group preferably contains carbon atoms in the range of 1 to 70.
  • a group containing a carbon atom in the range of 1 to 13 is more preferable.
  • R 1 group is, 1) R 1 group is, aliphatic and / or aromatic substituted 6 carbon atoms containing at least one kind may aromatic ring ⁇ 85, an N-substituted aromatic organic monourea in which an aromatic group in R 1 group is substituted by a ureido group and c is 1, and 2) R 1 group is aliphatic and / or aromatic An N-substituted aromatic organic group having 6 to 85 carbon atoms and containing at least one aromatic ring which may be substituted, wherein the aromatic group in R 1 group is substituted by a ureido group and c is 2 or more Polyurea, 3) N-substituted aliphatic organic polyurea in which R 1 group is an aliphatic group which has 1 to 85 carbon atoms and may be aromatic substituted, and c is 2 or 3.
  • the atom (mainly carbon) to which the ureido group is bonded is expressed as N-substituted aromatic organic urea when it is contained in the aromatic ring, and bonded to the atom (mainly carbon) that is not the aromatic ring.
  • N-substituted aliphatic organic urea More preferable aliphatic groups have 6 to 70 carbon atoms, and a chain hydrocarbon group, a cyclic hydrocarbon group, and at least one group selected from the chain hydrocarbon group and the cyclic hydrocarbon group are bonded to each other. (For example, a cyclic hydrocarbon group substituted with a chain hydrocarbon group, a chain hydrocarbon group substituted with a cyclic hydrocarbon group, etc.).
  • a method for producing the compound having a ureido group is a known method, for example, an organic primary amine, urea and / or a carbonic acid derivative (described in detail later) and / or isocyanic acid and / or N-unsubstituted. It can be obtained by reacting carbamic acid.
  • a compound having at least one ureido group derived from the organic primary amine and urea is obtained by ureido reaction of the organic primary amine and urea.
  • a manufacturing method is preferable, and in the present embodiment, it is preferable to use a compound having a ureido group obtained in a step including the following step A as the compound having a ureido group.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with c NH 2 groups, and c is an integer of 1 to 10.
  • the compound having a ureido group obtained in the step (A) is a compound having an ureido group having an organic group derived from the organic primary amine described above. That is, it is a step of reacting the organic primary amino group (—NH 2 ) of the organic primary amine with urea to generate the ureido group (this reaction is often referred to as a ureido reaction in this embodiment). .
  • the (—CONH 2 ) group in the ureido group (—NHCONH 2 ) is formed from the reacted urea.
  • the term “derived” is often used, but “derived” is used to mean that the group of the starting material is inherited when the functional group of the starting compound changes in the reaction. .
  • the compound having a ureido group has a structure in which the organic primary amino group (—NH 2 ) of the organic primary amine is converted.
  • (-CONH 2) group means that the reacted urea was contained in (NH 2 CONH 2) a (-CONH 2) group. Therefore, in the above formulas (1) and (3), a is preferably an integer equal to or less than c, and a and c are preferably the same integer.
  • the ureido group is a name of a substituent, and in this specification, “N-substituted (substituent name) urea” is described as a compound name.
  • N nitrogen atom
  • N-substituted is specified, and the substituent is an aromatic group, Or it is clearly an aliphatic group, and in the sense of an organic compound, “organic” is explicitly stated.
  • N-substituted aromatic organic monourea 1) R 1 group is a group having 6 to 85 carbon atoms and containing at least one aromatic ring which may be aliphatic and / or aromatically substituted, and R 1 N-substituted aromatic organic monourea in which the aromatic group in the group is substituted by a ureido group and c is 1, preferably the R 1 group is a group having 6 to 70 carbon atoms and c is 1
  • a certain aromatic organic monourea more preferably an N-substituted aromatic organic monourea in which R 1 is a group having 6 to 13 carbon atoms and c is 1 in consideration of fluidity and the like, N-substituted aromatic organic monourea represented by the following formula (41).
  • R 10 to R 13 groups may each independently substitute an aromatic ring, or R 10 to R 13 groups may be bonded to each other to form a ring together with the aromatic ring.
  • R 10 to R 13 groups may be formed of a hydrogen atom or a group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aryl groups having hydroxy groups, saturated aliphatic bonds and / or ethers.
  • N-substituted aromatic organic monourea represented by the formula (41) are groups in which R 10 to R 13 are selected from a hydrogen atom or an alkyl group such as a methyl group or an ethyl group.
  • N-substituted aromatic organic monoureas include N-phenylurea, N-tolylurea (each isomer), N-dimethylphenylurea (each isomer), N-diethylphenylurea (Each isomer), N-dipropylphenylurea (each isomer), N-naphthalene-ylurea (each isomer), N-methylnaphthalene-ylurea (each isomer), N-dimethylnaphthalene-ylurea (each isomer) ), N-trimethylnaphthalene-ylurea (each isomer), and the like.
  • N-phenylurea is
  • N-substituted aromatic organic polyurea has 6 to 85 carbon atoms in which the R 1 group contains one or more aromatic rings which may be aliphatic and / or aromatically substituted.
  • An N-substituted aromatic organic polyurea in which an aromatic group in R 1 group is substituted by a ureido group and c is 2 or more, preferably R 1 group has 6 to 6 carbon atoms 70 is an N-substituted aromatic organic polyurea having c of 2 or more, and in consideration of fluidity, the R 1 group preferably contains one or more aromatic rings.
  • the aromatic ring is an aromatic group having 6 to 13 carbon atoms which may be further substituted with an alkyl group, an aryl group or an aralkyl group, wherein a ureido group is bonded to the aromatic group contained in the R 1 group, c Is an N-substituted aromatic organic polyurea having 2 or more.
  • N, N′-phenylenediurea (each isomer), N, N′-methylphenylenediurea (each isomer), N, N′-methylenediphenylenediurea (each isomer), N , N′-mesitylenediurea (each isomer), N, N′-biphenyldiurea (each isomer), N, N′-dibenzyldiurea (each isomer), N, N′-propane-diylphenylenediurea ( Each isomer), N, N′-oxydiphenylenediurea (each isomer), N, N′-diphenyl-diyl-dipropane-diyldiurea (each isomer), N, N′-phenylenedimethylenediurea (each isomer) ), N, N′-methoxyphenylenediurea (each isomer),
  • R 1 group is an aliphatic group having 1 to 85 carbon atoms which may be aromatic substituted
  • c is 2 or 3 N-substituted aliphatic organic polyureas.
  • the aliphatic group is selected from a chain hydrocarbon group, a cyclic hydrocarbon group (including an aromatic group), and the chain hydrocarbon group and the cyclic hydrocarbon group.
  • N-substituted fat which is a group to which at least one group is bonded (for example, a cyclic hydrocarbon group substituted with a chain hydrocarbon group, a chain hydrocarbon group substituted with a cyclic hydrocarbon group, etc.) It is a group organic polyurea. More preferably, the R 1 group is an aliphatic group selected from an acyclic hydrocarbon group having 1 to 70 carbon atoms, a cyclic hydrocarbon group, and the acyclic hydrocarbon group and the cyclic hydrocarbon group.
  • a group to which at least one group is bonded (for example, a cyclic hydrocarbon group substituted with an acyclic hydrocarbon group, an acyclic hydrocarbon group substituted with a cyclic hydrocarbon group, etc.).
  • N is an N-substituted aliphatic organic polyurea in which c is 2 or 3.
  • the R 1 group is an acyclic hydrocarbon group having 6 to 13 carbon atoms composed of a carbon atom and a hydrogen atom, or cyclic carbonization.
  • a hydrogen group, and a group in which at least one group selected from the acyclic hydrocarbon group and the cyclic hydrocarbon group is bonded for example, a cyclic hydrocarbon group substituted with an acyclic hydrocarbon group, a ring N-substituted aliphatic organic polyurea which is an acyclic hydrocarbon group substituted with a formula hydrocarbon group.
  • the R 1 group is a linear and / or branched alkyl group, a cycloalkyl group, and a group composed of the alkyl group and the cycloalkyl group.
  • Examples thereof include methylene diurea, 1,2-dimethylene diurea, 1,3-trimethylene diurea, 1,4-tetramethylene diurea, 1,5-pentamethylene diurea, 1,6-hexamethylene diurea, 1, 8-octamethylenediurea, cyclopentane-diurea (each isomer), cyclohexane-diurea (each isomer), cycloheptane-diurea (each isomer), cyclooctane-diurea (each isomer), methylcyclopentane-diurea (Each isomer), ethylcyclopentane-diurea (each isomer), methylcyclohexane-diurea (each isomer), ethylcyclohexane-diurea (each isomer), propylcyclohexane-diurea (each iso
  • step (A) in addition to the organic primary amine and urea, water and / or alcohol and / or an aromatic hydroxy composition (at least one aromatic hydroxy It may be carried out in the presence of a composition containing the compound).
  • step (A) When it is performed in the presence of an aromatic hydroxy composition, it is performed in the presence of the above-described aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the following formula (2)). Is preferred.
  • step (R) esteerification reaction step
  • step (P) transesterification reaction step
  • the alcohol used in the present embodiment is preferably an alcohol represented by the following formula (4).
  • R 2 group represents an aliphatic group containing an integer number of carbon atoms in the range of 1 to 14 or a group composed of an aliphatic group to which an aromatic group is bonded.
  • the OH group of the alcohol represented by formula (4) is an aromatic group. An OH group not bonded to a group ring.
  • a preferred alcohol represented by the formula (4) is a group in which the R 2 group is an aliphatic group or an aliphatic group bonded with an aromatic group, and the OH group of the alcohol represented by the formula (4) Is an alcohol which is an OH group not bonded to an aromatic group.
  • the R 2 group is an acyclic hydrocarbon group, a cyclic hydrocarbon group (for example, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, a ring assembly carbon group).
  • the R 2 group that can be preferably used in the present embodiment is selected from an aliphatic group to which an aliphatic group and / or an aromatic group are bonded, considering the difficulty of side reactions.
  • step (P) in the present embodiment it is preferable to transesterify the N-substituted carbamic acid-O—R 2 ester with the aromatic hydroxy composition to remove by-produced alcohol out of the system.
  • the alcohol used in (A) and / or step (R) preferably has a lower boiling point than the aromatic hydroxy compound contained in the aromatic hydroxy composition, and more preferably has 1 to 10 carbon atoms. It is a group containing. More preferably, it is a group containing carbon atoms in the range of 1 to 8. More preferable R 2 is an alkyl group, a group in which a cycloalkyl group and an alkyl group are bonded, or an aralkyl group.
  • Examples of such preferred alcohols include methanol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), hexanol (each isomer), heptanol (each isomer), Examples include octanol (each isomer), benzyl alcohol, tolyl methanol (each isomer), xylyl methanol (each isomer), phenylethyl alcohol (each isomer), and the like.
  • R 2 is an alkyl group among the alcohols shown above, and among the carbon atoms constituting the alkyl group, the ⁇ -position carbon atom of the hydroxy group (the carbon atom constituting the alkyl group).
  • a carbon atom to which an OH group is bonded is a secondary (—CH 2 —) alcohol.
  • the aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the formula (2)) used in this embodiment will be described.
  • ⁇ Aromatic hydroxy composition> there are many methods and steps for using the aromatic hydroxy composition. It is used as a compound constituting the composition for transporting and storing the above-described compound having a ureido group. Moreover, it is also preferable to implement a process (A) in presence of an aromatic hydroxy composition (a composition containing the aromatic hydroxy compound represented by at least 1 sort (s) of Formula (2)). Moreover, the aromatic hydroxy composition (composition containing at least one aromatic hydroxy compound represented by the formula (2)) is also used in the step (P) mentioned in the description of the alcohol.
  • step (A) (ureido reaction step) and the following step (B) a method of obtaining N- substituted carbamic acid -O- aryl ester in a process including (esterification step) is
  • an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by formula (2)) is used.
  • an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by formula (2)) may be used.
  • the aromatic hydroxy composition used is an aromatic hydroxy composition using at least one aromatic hydroxy compound represented by the above formula (2).
  • the aromatic hydroxy composition in the present embodiment is a composition containing one kind of aromatic hydroxy compound or plural kinds of aromatic hydroxy compounds.
  • the aromatic hydroxy compound which is preferably used as the aromatic hydroxy compound constituting the aromatic hydroxy composition will be described.
  • the aromatic hydroxy compound constituting (containing) the aromatic hydroxy composition is at least one aromatic hydroxy compound represented by the following formula (2).
  • Ring A represents an organic group containing 6 to 50 carbon atoms containing an aromatic group substituted with b hydroxy groups at any position that maintains aromaticity, and is monocyclic, multicyclic or heterocyclic. Or may be substituted with other substituents, and b is an integer of 1 to 6.
  • the substituent for substituting the aromatic group of the aromatic hydroxy compound represented by the above formula (2) is selected from a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, and a group to which the above group is bonded.
  • An acyclic hydrocarbon group, a cyclic hydrocarbon group for example, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, a ring assembly hydrocarbon group, a side A cyclic hydrocarbon group having a chain, a heterocyclic group, a heterocyclic spiro group, a hetero-bridged cyclic group, a heterocyclic group), a group selected from the acyclic hydrocarbon group and the cyclic hydrocarbon group And a group in which one or more types are bonded to each other through a covalent bond with a specific nonmetallic atom (carbon, oxygen, nitrogen, sulfur, silicon).
  • the covalent bond with the specific nonmetallic atom is, for example, a group represented by the following formulas (8) to (11), (13) to (16) This is a state in which the above groups are bonded by a covalent bond.
  • Ring A is a structure containing at least one structure selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring, and preferably ring A is at least selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring It is a structure containing one structure, More preferably, ring A is a structure containing one benzene ring.
  • substituents that can be preferably used in the present embodiment are acyclic hydrocarbon groups, cyclic hydrocarbon groups (monocyclic hydrocarbon groups) in view of the difficulty of side reactions.
  • a compound having a ureido group and / or an N-substituted carbamic acid-O—R 2 ester and an aromatic hydroxy composition Is reacted at a high temperature to obtain an N-substituted carbamic acid-O-aryl ester, in addition to the aromatic group and the hydroxy group bonded to the aromatic group, It is preferably an aromatic hydroxy compound composed of a group having at least one inert substituent (including a hydrogen atom) (wherein the inert substituent is, for example, a phenyl group and It shows a substituent that does not have an active hydrogen with a pKa of a bound compound of 30 or less (however, it may have an aromatic hydroxyl group).
  • the aromatic hydroxy compound represented by the formula (2) is at least selected from the group of substituents shown below in addition to the aromatic group and the hydroxy group bonded to the aromatic group.
  • An aromatic hydroxy compound having one substituent. (I) a hydrogen atom, (Ii) a group composed of a carbon atom and a hydrogen atom (which may be further combined with ring A to form a ring structure); (Iii) a group composed of a carbon atom, a hydrogen atom and an oxygen atom (for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group) Represents an ether group (however, carbonyl group, ester group, terminal methine group and alcoholic OH group, carboxyl group, NH 2 group, NH group, NOH group, SH group, SO 3 H group, SOH group, etc.) Except for groups containing hydrogen), (Iv)
  • Active hydrogen refers to a hydrogen atom bonded to oxygen, nitrogen, sulfur or nitrogen (excluding an aromatic hydroxyl group).
  • An aromatic hydroxyl group (an OH group directly bonded to an aromatic group) is a group included in the definition of active hydrogen, but the aromatic hydroxyl group is included in the composition and reaction raw material of the present embodiment.
  • the group containing active hydrogen does not contain an aromatic hydroxyl group. Often referred to as the “group containing active hydrogen” elsewhere in the present invention, the above definition applies.
  • Ring A is a structure containing at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and an anthracene ring, and is preferably an aromatic hydroxy compound represented by the following formula (7).
  • Ring A is an aromatic ring selected from a benzene ring, a naphthalene ring, and an anthracene ring
  • the OH group and R 7 to R 14 groups each represent a group that substitutes at any position that maintains the aromaticity of ring A.
  • R 7 to R 14 may each independently replace ring A, or R 7 to R 14 may be bonded together to form a ring together with ring A.
  • R 7 to R 14 Each independently represents a hydrogen atom or a halogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aryl group having a hydroxy group, an aralkyl group, an ether group (substituted and / or unsubstituted alkyl ether and / or aryl).
  • a group group selected from said group is selected from the group consisting a group bonded through a saturated aliphatic bond and / or an ether bond, R 14 from a ring A and R 7, the total carbon number of 6 50 It consists of an integer number in the range of.
  • b represents an integer of 1 to 6
  • d, e, f, g, h, i, j, k represents an integer of 0 to 5
  • the value of d + e + f + g + h + i + j + k is the value when ring A is a benzene ring; 6 ⁇ b And when ring A is a naphthalene ring; an integer of 8-b and when ring A is an anthracene ring; an integer of 10-b is represented.
  • a group selected from R 7 to R 14 may be cyclically bonded to ring A through a carbon-carbon bond and / or an ether bond.
  • a compound that forms an aryl ester ie, the O-aryl group that forms the carbamic acid-O-aryl ester group is formed with the aromatic hydroxy compound, and the N-substituted carbamic acid group moiety has the ureido group
  • N-substituted carbamic acid-O-aryl ester formed from the N-substituted carbamic acid-O—R 2 ester when the step (P) is carried out, and the N-substituted carbamic acid-O—R 2 ester is subjected to an ester exchange reaction.
  • N- substituted carbamic acid -O-R 2 ester i.e. The N- substituted carbamic acid -O- aryl ester, the N- O-alkyl ester of substituted carbamate -O-R 2 ester and aromatic hydroxy compound and an ester interchange N- substituted carbamic acid -O-R 2 ester).
  • the N-substituted carbamic acid-O-aryl ester is used as an isocyanate precursor. The method for producing an isocyanate derived from the N-substituted carbamic acid-O-aryl ester will be described in detail later.
  • the N-substituted carbamic acid-O-aryl ester obtained in the step of the present embodiment is converted into the following step: It is preferable to obtain an isocyanate and aromatic hydroxy composition represented by the following formula (6) derived from the N-substituted carbamic acid-O-aryl ester by thermal decomposition with (F).
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with s NCO groups, and s is an integer of 1 to 10.
  • the N-substituted carbamic acid-O-aryl ester is thermally decomposed to obtain an aromatic hydroxy compound derived from the N-substituted carbamic acid-O-aryl ester and an isocyanate.
  • the isocyanate derived from the N-substituted carbamic acid-O-aryl ester is a carbamate O-aryl group of the N-substituted carbamic acid-O-aryl ester (—NHCOOAr; Ar in the group is This represents an isocyanate compound obtained by converting an aryl group derived from an aromatic hydroxy compound into an isocyanate group (—NCO).
  • the aromatic hydroxy compound produced in that case is considered to be the aromatic hydroxy compound contained in the aromatic hydroxy composition that is reacted with the compound having a ureido group when obtaining the N-substituted carbamic acid-O-aryl ester.
  • Group hydroxy compounds That is, the aromatic hydroxy compound of formula (2), preferably of formula (7), is by-produced with isocyanate during the thermal decomposition of the N-substituted carbamic acid-O-aryl ester. After the thermal decomposition step, depending on the case, as one of the embodiments, the aromatic hydroxy compound and the isocyanate are separated by distillation, and the separated aromatic hydroxy compound is a compound having a ureido group.
  • the aromatic hydroxy composition to be reacted may be recycled. That is, the aromatic hydroxy composition obtained in the step (F) is separated from the isocyanate, and the step (A) and / or the step (B), or the step (A) and / or the step (R) and / or the step. Recycling to (P) is a preferred embodiment.
  • the aromatic hydroxy compound as the raw material of the N-substituted carbamic acid-O-aryl ester and the N-substituted carbamic acid-O-aryl It is necessary to consider the separability from the isocyanate formed from the ester. Although it is difficult to generally define the separability, it is usually defined based on the knowledge that the two components to be separated can be sufficiently separated by distillation if the standard boiling points of the two components are separated by 10 ° C. or more. Therefore, this definition is a value limited to currently known separation means, and is not a definition that forms the basis of the present embodiment.
  • the aromatic hydroxy compound constituting the aromatic hydroxy composition used in the present embodiment includes a compound having a ureido group and / or an N-substituted carbamic acid-O—R 2 ester (the N-substituted carbamic acid-O—).
  • the R 2 ester will be described in detail later), and / or the reactivity with urea or the like is important, while the standard boiling point is an important selection index for separation from each component.
  • the boiling point of the aromatic hydroxy compound is greatly affected by the type and number of substituents, the position of the substituents, and the like.
  • the boiling point is a physical property that also depends on the intermolecular force and cannot be defined only by the structure of one molecule. Therefore, the selection of the aromatic hydroxy compound based on the normal boiling point, which is one aspect of the present embodiment described above, measures the structure and properties (standard boiling point) of the desired N-substituted carbamic acid-O-aryl ester and / or isocyanate. Or research and select.
  • the standard boiling point can be measured by a known method, and can usually be carried out by a researcher in the field.
  • the separation of the aromatic hydroxy compound used in the present embodiment it is difficult to define it by a structure such as a general formula, and the intended method of the present embodiment is an aromatic hydroxy compound. It is not to predict the normal boiling point of a compound. Therefore, as described above, this embodiment can be carried out by those skilled in the art by referring to or measuring the standard boiling point according to the compound used.
  • the organic primary amine represented by the above-described formula (3) and the above-described urea are subjected to a ureido reaction in the step (A), and the formula ( A compound having a ureido group shown in 1) is obtained, and the compound having an ureido group and an aromatic hydroxy composition (at least one type of aromatic hydroxy compound represented by formula (2) (preferably formula (7)) And an esterification reaction by carrying out step (B) to obtain a compound having an N-substituted carbamic acid-O-aryl ester group.
  • Step (F) is used to produce an aromatic hydroxy compound and an isocyanate derived from the N-substituted carbamic acid-O-aryl ester.
  • an aromatic hydroxy compound and an isocyanate derived from the N-substituted carbamic acid-O-aryl ester are produced by a method including the step (A), the step (R), the step (P) and the step (F).
  • the organic primary amine is an aromatic organic monoprimary amine represented by the following formula (5), and the following step (C) is performed after the step (B) or the step (P) (step ( C) will be described in detail later), from the N-substituted carbamic acid-O-aryl ester obtained in step (B) or (P), at least two molecules of the N-substituted carbamic acid-O-aryl
  • An N-substituted carbamic acid-O-aryl ester in which the ester is bridged with a methylene group (—CH 2 —) is obtained, and then step (F) is performed to convert the N-substituted carbamic acid-O-aryl ester to The derived aromatic hydroxy compound and isocyanate are produced.
  • At least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are obtained by crosslinking an aromatic group derived from an aromatic organic monoprimary amine contained in the ester with a methylene group (—CH 2 —).
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring a substituted to group at any position to keep the ring from R 3 may be substituted an aromatic ring each independently R 6 groups, also with an aromatic ring from R 3 by bonding R 6 originally between R 3 to R 6 groups may be hydrogen atoms or groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aryl groups having hydroxy groups, saturated aliphatic bonds and / or An aromatic group represented by the formula (5), which is a group selected from a group composed of ether-bonded groups, wherein R 3 to R 6 have an integer of 0 to 7 carbon atoms.
  • the total number of carbon atoms constituting the organic mono primary amine is 6 to 1 It consists of an integer number of. )
  • N-substituted carbamic acid-O— (R 2 or aryl) ester is often used, but “N-substituted carbamic acid-O—R 2 ester or N-substituted carbamic acid-O” is used. Means “aryl ester”.
  • the structure of the aromatic hydroxy compound and isocyanate to be separated after the thermal decomposition reaction is the aromatic hydroxy compound used when the compound having a ureido group is an N-substituted carbamic acid-O-aryl ester.
  • An aromatic hydroxy compound constituting (containing in) the hydroxy composition, and one product, isocyanate is a compound having a ureido group represented by formula (1) or an organic compound represented by formula (3) Derived from a primary amine (that is, a ureido group (—NHCONH 2 ) of a compound having a ureido group is used as an isocyanate group (—NCO), or a primary amino group (—NH 2 ) of an organic primary amine is used as an isocyanate group.
  • An isocyanate having a structure of (—NCO) is obtained).
  • the isocyanate represented by the formula (6) obtained by the method of the present embodiment is produced using a compound having a ureido group or an organic primary amine as a starting material.
  • the normal boiling point may be the standard boiling point of an isocyanate in which all of the ureido group or primary amino group of the compound having an ureido group or an organic primary amine are converted to an isocyanate group.
  • the compound having a ureido group is a compound having a ureido group obtained by carrying out the step (A). That is, the normal boiling point of the aromatic hydroxy compound constituting the aromatic hydroxy composition is the normal boiling point of an isocyanate having a structure in which all amino groups (first amino groups) of the organic primary amine are converted to isocyanate groups, Aromatic hydroxy compounds that differ by 10 ° C. or more are preferred.
  • an aromatic monohydroxy compound having a benzene ring as a nucleus as it is easily available is preferable.
  • an aromatic monohydroxy compound represented by the following formula (31) is preferable.
  • R 19 , R 20 , R 21 , R 22 , and R 23 are groups independently selected from the above R 7 to R 14 groups (excluding aryl groups having a hydroxy group)
  • the aromatic hydroxy compound represented by 31 is an aromatic monohydroxy compound having an integer of 6 to 50 carbon atoms. That is, the total number of carbon atoms in the R 19 , R 20 , R 21 , R 22 , and R 23 groups is an integer of 0 to 44.
  • R 19 , R 20 , R 21 , R 22 , R 23 groups are hydrogen atoms and / or the following (i) to (iii): Each group is independently selected from the groups shown.
  • Atom alkyl group having 1 to 43 carbon atoms, cycloalkyl group having 4 to 44 carbon atoms, alkoxy group having 1 to 44 carbon atoms, polyoxyalkylene alkyl ether group having 2 to 44 carbon atoms and having no OH group at the terminal
  • a group bonded to three atoms (Ii) an aryl group having 1 to 44 carbon atoms, wherein the aryl group is substituted with a substituent, and the substituent may be substituted with the following substituent in the range of an integer of 1 to 5
  • An aryl group, and the substituent is a hydrogen atom, an alkyl group having 1 to 38 carbon atoms, a cycloalkyl group having 4 to 38 carbon atoms, an alkoxy group having 1 to 38 carbon atoms, or a terminal group having 2 to 38 carbon atoms.
  • the term “ ⁇ -position atom” is used, and the “ ⁇ -position atom” means an atom constituting R 19 , R 20 , R 21 , R 22 , R 23.
  • the R 19 , R 20 , R 21 , R 22 , and R 23 are atoms adjacent to the carbon atom on the aromatic hydrocarbon ring to which the group is bonded.
  • R 19 , R 20 , R 21 , R 22 and R 23 groups include hydrogen atom, methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each Isomer), hexyl group (each isomer), heptyl group (each isomer), octyl group (each isomer), nonyl group (each isomer), decyl group (each isomer), dodecyl group (each isomer) ), Octadecyl group (each isomer), cyclopentane, cyclohexane, cycloheptane, cyclooctane, bis (cyclohexyl) alkane, methylcyclopentane (each isomer), ethylcyclopentane (each isomer), methylcyclohexane (each isomer)
  • Examples of preferred aromatic monohydroxy compounds represented by the above formula (30) include the following. Phenol, methylphenol (each isomer), ethylphenol (each isomer), propylphenol (each isomer), butylphenol (each isomer) pentylphenol (each isomer), hexylphenol (each isomer), heptylphenol (Each isomer), octylphenol (each isomer), nonylphenol (each isomer), decylphenol (each isomer), dodecylphenol (each isomer), octadecylphenol (each isomer), Dimethylphenol (each isomer), diethylphenol (each isomer), dipropylphenol (each isomer), dibutylphenol (each isomer), dipentylphenol (each isomer), dihexylphenol (each isomer), di Heptylphenol (each is
  • R 19 , R 20 , R 21 , R 22 , and R 23 are hydrogen atoms, and R 19 ,
  • the number of carbon atoms constituting the R 20 , R 21 , R 22 , R 23 group is more preferably 0-13.
  • the R 20 , R 21 , R 22 , R 23 group is a group having 0 to 9 carbon atoms, and is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a substituted or An aromatic monohydroxy compound which is a group selected from an unsubstituted aryl group, a linear or branched alkoxy group, a substituted or unsubstituted aryloxy group, and a substituted or unsubstituted aralkyl group.
  • the aromatic hydroxy compound represented by the formula (2) and / or the formula (7) and / or the formula (31) is an aromatic composition used for a composition for transferring and storing a compound having a ureido group. Can be suitably used as an aromatic hydroxy compound. Also, an aromatic hydroxy composition used for producing an N-substituted carbamic acid-O-aryl ester by reacting with a compound having a ureido group and / or an N-substituted carbamic acid-O-R 2 ester It can also be suitably used as an aromatic hydroxy compound.
  • the latter aromatic hydroxy compound constituting the aromatic hydroxy composition used for the production of the N-substituted carbamic acid-O-aryl ester is a compound having a ureido group and / or N-substituted carbamic acid-O.
  • composition for transporting and storing the compound having a ureido group is used as a raw material of an N-substituted carbamic acid-O-aryl ester, or a compound having a ureido group is used as a raw material, an N-substituted carbamic acid-O—
  • an aromatic hydroxy compound that is included in the formula (7) and / or the formula (31) but is represented by the following formula (32) (in order to express the ease of the reaction).
  • an aromatic hydroxy compound represented by the following formula (32) is often referred to as an “active aromatic hydroxy compound”.
  • the active aromatic hydroxy compound represented by the following formula (32) may be used alone as an aromatic hydroxy composition used for a composition for transferring and storing a compound having a ureido group, or an aromatic hydroxy composition. You may use as an aromatic hydroxy compound which comprises a thing. Further, an active aromatic hydroxy compound represented by the following formula (32) is reacted with a compound having a ureido group and / or an N-substituted carbamic acid-O—R 2 ester to give an N-substituted carbamic acid-O-aryl.
  • the active aromatic monohydroxy compound is represented by the following formula (32).
  • Ring A represents an organic group containing an aromatic group substituted with b hydroxy groups at any position that retains aromaticity, and may be a single ring, a plurality of rings, a heterocyclic ring, or other substituents.
  • the OH group represented by the formula (32) is substituted with an integer of 1 to 6 on the aromatic ring contained in the ring A. (That is, the above formula (32) shows a part of the ring A, and the structure in which the R 24 group, the OH group, and the R 25 group shown above are adjacent to each other is an integer in the range of 1 to 6 on the ring A. It shows that there are.
  • R 24 and R 25 are groups bonded to the aromatic ring to which the hydroxy group is bonded, and are bonded to the carbon adjacent to the carbon to which the hydroxy group is bonded.
  • the hydroxy group is bonded to ring A by an integer of 1 to 6, and thus R 24 and R 25 are each bonded to ring A by an integer of 1 to a maximum of 6.
  • the aromatic hydroxy compound represented by the formula (32) is an aromatic hydroxy compound containing an integer number of carbon atoms in the range of 6 to 50. )
  • a hydrogen atom, a halogen atom, a fatty acid Selected from the group consisting of an aromatic group, an aromatic group, and an aliphatic group to which an aromatic group is bonded an acyclic hydrocarbon group, a cyclic hydrocarbon group (for example, a monocyclic hydrocarbon group, a condensed polycyclic carbon group) Hydrogen group, bridged cyclic hydrocarbon group, spiro hydrocarbon group, ring assembly hydrocarbon group, cyclic hydrocarbon group with side chain, heterocyclic group, heterocyclic spiro group, hetero bridged cyclic group, heterocyclic group)
  • the covalent bond with the specific nonmetallic atom is, for example, a group represented by the above formulas (8) to (11), (13) to (16) And the above-described groups are bonded by a covalent bond.
  • substituents that can be preferably used in the present embodiment are acyclic hydrocarbon groups, cyclic hydrocarbon groups (monocyclic hydrocarbon groups) in view of the difficulty of side reactions.
  • a composition containing a compound having a ureido group is transferred at a high temperature
  • a compound having a ureido group and / or an N-substituted carbamic acid-O—R 2 ester is reacted with an aromatic hydroxy composition.
  • the reaction for obtaining the N-substituted carbamic acid-O-aryl ester is carried out at high temperature
  • the ring A of the aromatic hydroxy compound is an inert substituent in addition to the aromatic group and the hydroxy group bonded to the aromatic group.
  • an aromatic hydroxy compound composed of a group having at least one (including hydrogen atom) (wherein the inert substituent is a group in which the inert substituent does not include the active hydrogen described above)
  • the inert substituent is a group in which the inert substituent does not include the active hydrogen described above
  • it may have an aromatic hydroxyl group
  • the aromatic hydroxy compound represented by the formula (32) includes the following (i) to (v) in addition to the aromatic group and the hydroxy group bonded to the aromatic group.
  • active hydrogen such as carbonyl group, ester group, terminal methine group and alcoholic OH group, carboxyl group, NH 2 group, NH group, NOH group, SH group, SO 3 H group, SOH group, etc.
  • a halogen atom a group composed of an atom selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom (however, a carbonyl group, an ester group, a terminal methine group and an alcoholic OH group, a carboxyl group) , NH 2 groups, NH groups, NOH groups, SH groups, SO 3 H groups, and groups containing active hydrogen such as SOH groups are excluded).
  • R 24 and R 25 are each independently any one group defined by the following (i) to (v), and R 24 and R 25 are bonded to A to form a condensed ring structure. May be.
  • the relationship between the ring A and the hydroxyl group is a structure represented by the following formula (33) or the following formula (34), it is adjacent to the OH group bonded to the aromatic group constituting the ring A.
  • the number of R 24 and R 25 bonded to the carbon to be bonded does not match the number of the OH groups, but in the structure represented by the following formula (33), ring A is represented by the following formula (35).
  • R 25 may be bonded to ring A to form a ring structure.
  • the aromatic hydroxyl group bonded to the ring A may be a central OH group, and adjacent OH groups may be R 24 and R 25 groups, respectively.
  • the carbon at the ⁇ -position has a double bond or triple bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 24 and R 25 ). Also when formed, the ⁇ -position carbon atom may be tertiary or quaternary.
  • (Iii) a group composed of a carbon atom, a hydrogen atom and an oxygen atom (for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group) Represents an ether group, provided that it is an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, or a group having no methine group at the terminal, and is in the ⁇ position (the atoms forming the R 24 and R 25 ) Among them, an atom of an atom bonded to the aromatic ring of ring A) is a carbon atom or an oxygen atom, and in the case of a carbon atom, it is a primary or secondary carbon atom (that is, carbon of a methyl group, Represents the carbon forming the —CH 2 — bond).
  • an atom of an atom bonded to the aromatic ring of ring A is a carbon atom
  • the carbon atom at the ⁇ -position is It may be tertiary or quaternary, and the ⁇ -position carbon is in the ⁇ -position (of the atoms forming the R 24 and R 25 , the atoms bonded to the aromatic ring of the ring A Even when a double bond or a triple bond is formed with the adjacent atom, the carbon atom at the ⁇ -position may be tertiary or quaternary.
  • a halogen atom (V) a group composed of an atom selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom (however, an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, a terminal methine group) , NH 2 group, NH group, NOH group, SH group, SO 3 H group, and other groups containing active hydrogen such as SOH group, and the ⁇ -position (the atoms forming R 24 and R 25 )
  • the atom of the ring A bonded to the aromatic ring is a carbon atom, an oxygen atom or a sulfur atom, and in the case of a carbon atom, a primary or secondary carbon atom (that is, a methyl group) Carbon represents a carbon that forms a —CH 2 — bond), and in the case of a sulfur atom, it is a divalent
  • the carbon atom at the ⁇ -position is It may be tertiary or quaternary, and the ⁇ -position carbon is in the ⁇ -position (of the atoms forming the R 24 and R 25 , the atoms bonded to the aromatic ring of the ring A In the case where a double bond or a triple bond is formed with the adjacent atom, the carbon atom at the ⁇ -position may be tertiary or quaternary.
  • active hydrogen refers to a hydrogen atom bonded to oxygen, nitrogen, sulfur, or nitrogen.
  • aromatic hydroxyl groups are excluded.
  • An aromatic hydroxyl group (an OH group directly bonded to an aromatic group) is also an active hydrogen, but the aromatic hydroxyl group is also included in the composition and reaction raw material of the present embodiment, and has an adverse effect.
  • aromatic hydroxyl groups are excluded from the groups containing active hydrogen. Although often referred to as the “group containing active hydrogen” in other parts of this embodiment, the above definition applies.
  • Such active hydrogen is highly reactive, and organic primary amines and urea compounds used in this embodiment, compounds having a ureido group and N-substituted carbamic acid-O produced in this embodiment are used. It is not preferable because it may react with a-(R 2 or aryl) ester to produce a side reaction product.
  • a structure in which the ring A contains at least one structure selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring is preferable.
  • the step (F) (often referred to as a thermal decomposition step, thermal decomposition, or thermal decomposition) is performed, the equations (2), (7), (31), and (32)
  • the indicated aromatic hydroxy compound is by-produced with the isocyanate during thermal decomposition of the N-substituted carbamic acid-O-aryl ester.
  • the aromatic hydroxy compound and the isocyanate may be separated by distillation and recycled as the aromatic hydroxy composition of the present embodiment. Good.
  • the standard boiling point serves as an index, and is selected according to the above definition.
  • aromatic monohydroxy compounds that are easily available are preferred in view of industrial use.
  • aromatic monohydroxy compound represented by the following formula (38) is preferable.
  • R 28 , R 29 , and R 30 are groups independently selected from the aforementioned R 7 to R 14 groups (excluding aryl groups having a hydroxy group), and R 26 and R 27 groups are
  • the aromatic hydroxy compound represented by the formula (38) is an aromatic monohydroxy compound having an integer of 6 to 50 carbon atoms, each of which is independently selected from the aforementioned R 24 and R 25 groups. . That is, the total carbon number of R 26 , R 27 , R 28 , R 29 and R 30 groups is an integer of 0 to 44.
  • R 26 and R 27 are each independently any one group defined in the following (i) to (iii).
  • R 26 and R 27 are groups independently selected from the aforementioned R 24 and R 25 groups, and are each independently any one group defined by (i) to (iii) below. .
  • the carbon atom is a primary or secondary carbon atom (that is, a carbon atom of a methyl group,- Represents a carbon that forms a CH 2 — bond).
  • the ⁇ -position carbon atom May be grade 3 or grade 4.
  • the carbon at the ⁇ -position has a double bond or a triple bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 26 and R 27 ).
  • the ⁇ -position carbon atom may be tertiary or quaternary.
  • (Iii) a group composed of a carbon atom, a hydrogen atom and an oxygen atom (for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group) Represents an ether group, provided that it is an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, or a group having no methine group at the terminal, and is in the ⁇ position (the atoms forming the R 26 and R 27 ) Among them, an atom of an atom bonded to the aromatic ring of ring A) is a carbon atom or an oxygen atom, and in the case of a carbon atom, it is a primary or secondary carbon atom (that is, carbon of a methyl group, Represents the carbon forming the —CH 2 — bond).
  • an atom of an atom bonded to the aromatic ring of ring A is a carbon atom
  • the ⁇ -position carbon atom May be tertiary or quaternary, and the carbon at the ⁇ -position is in the ⁇ -position (the atom bonded to the aromatic ring of the ring A among the atoms forming the R 26 and R 27 In the case where a double bond or a triple bond is formed with the next atom), the ⁇ -position carbon atom may be tertiary or quaternary.
  • Preferred active aromatic monohydroxy compounds are the R 26 And R 27
  • examples of such aromatic monohydroxy compounds include phenol, methylphenol (each isomer), ethylphenol (each isomer), 2-n-propylphenol (each isomer).
  • R 26 And R 27 Aromatic monohydroxy compounds or naphthols (each isomer), phenoxyphenol (each isomer), diphenoxy-phenol (wherein the group is a hydrogen atom and the other substituent is a linear and / or cyclic saturated alkyl group) Each isomer).
  • the substituent in which the ⁇ -position atom is a tertiary or quaternary carbon atom or a tertiary nitrogen atom is bonded to at least one ortho position with respect to the hydroxyl group of the aromatic hydroxy compound.
  • N-substituted carbamic acid-O-aryl ester varies depending on the type of aromatic hydroxy compound, and the following types of aromatic compounds
  • a process for producing an N-substituted carbamic acid-O-aryl ester using an aromatic hydroxy composition containing an aromatic hydroxy compound was also conceived and completed.
  • the aromatic hydroxy compound described below is a method for producing an N-substituted carbamic acid-O-aryl ester using an aromatic hydroxy composition containing a plurality of types of aromatic hydroxy compounds.
  • a low activity aromatic hydroxy compound for use in a process for producing an N-substituted carbamic acid-O-aryl ester using an aromatic hydroxy composition comprising a low activity hydroxy compound That is, the above-described aromatic hydroxy compound (active aromatic hydroxy compound) having a high production rate of N-substituted carbamic acid-O-aryl ester and the production rate of N-substituted carbamic acid-O-ester
  • a method for producing N-substituted carbamic acid-O-esters using an aromatic hydroxy composition comprising a low aromatic hydroxy compound hereinafter often referred to as a low activity aromatic hydroxy compound).
  • the low activity aromatic hydroxy compound described above is represented by the following formula (39).
  • Ring A represents an organic group containing an aromatic group substituted with b hydroxy groups at any position that retains aromaticity, and may be a single ring, a plurality of rings, a heterocyclic ring, or other substituents.
  • the OH group represented by the formula (39) is substituted with an integer of 1 to 6 on the aromatic ring contained in the ring A. (That is, the above formula (39) shows a part of the ring A, and the structure in which the R 31 group, the OH group, and the R 32 group shown above are adjacent to each other is an integer in the range of 1 to 6 on the ring A. It shows that there are.
  • R 31 and R 32 are groups that replace the aromatic ring to which the hydroxy group is bonded, and are groups that bond to a carbon adjacent to the carbon to which the hydroxy group is bonded.
  • the hydroxy group is bonded to ring A by an integer of 1 to 6, and thus R 31 and R 32 are each bonded to ring A by an integer of 1 to a maximum of 6.
  • the aromatic hydroxy compound represented by the formula (39) is an aromatic hydroxy compound containing an integer number of carbon atoms in the range of 6 to 50. )
  • a hydrogen atom, a halogen atom, a fatty acid Selected from aromatic groups and aromatic groups acyclic hydrocarbon groups, cyclic hydrocarbon groups (eg monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, bridged cyclic hydrocarbon groups, spiro hydrocarbons) Group, ring assembly hydrocarbon group, cyclic hydrocarbon group with side chain, heterocyclic group, heterocyclic spiro group, hetero-bridged cyclic group, heterocyclic group), the acyclic hydrocarbon group and the above A group in which at least one kind selected from a group selected from cyclic hydrocarbon groups is bonded, and a group in which the group is bonded through a covalent bond with a specific nonmetallic atom (carbon, oxygen, nitrogen, sulfur, silicon) Represents.
  • a specific nonmetallic atom carbon, oxygen, nitrogen, sulfur, silicon
  • the covalent bond with the specific nonmetallic atom is, for example, a group represented by the above formulas (8) to (11), (13) to (16) And the above-described groups are bonded by a covalent bond.
  • substituents that can be preferably used in the present embodiment are acyclic hydrocarbon groups, cyclic hydrocarbon groups (monocyclic hydrocarbon groups) in view of the difficulty of side reactions.
  • a composition containing a compound having a ureido group is transferred at a high temperature
  • a compound having a ureido group and / or an N-substituted carbamic acid-O—R 2 ester is reacted with an aromatic hydroxy composition.
  • the reaction for obtaining the N-substituted carbamic acid-O-aryl ester is carried out at a high temperature
  • the ring A of the aromatic hydroxy compound is an inert substituent in addition to the aromatic group and the hydroxy group bonded to the aromatic group.
  • an aromatic hydroxy compound composed of a group having at least one (including hydrogen atom) (wherein the inert substituent is a group in which the inert substituent does not include the active hydrogen described above)
  • the inert substituent is a group in which the inert substituent does not include the active hydrogen described above
  • it may have an aromatic hydroxyl group
  • the aromatic hydroxy compound represented by the formula (39) is represented by the following (i) to (v) in addition to the aromatic group and the hydroxy group bonded to the aromatic group.
  • an active hydrogen such as a SOH group Group
  • a halogen atom a group composed of an atom selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom (however, a carbonyl group, an ester group, a terminal methine group and an alcoholic OH group, a carboxyl group) , NH 2 groups, NH groups, NOH groups, SH groups, SO 3 H groups, and groups containing active hydrogen such as SOH groups are excluded).
  • R 31 and R 32 are each independently any one group defined by the following (i) to (viii), and at least one of them is a group defined by the following (vi) to (viii) Furthermore, R 31 and R 32 may combine with A to form a condensed ring structure.
  • R 31 and R 32 may combine with A to form a condensed ring structure.
  • the number of R 31 and R 32 bonded to the carbon adjacent to the OH group due to the relationship between ring A and the hydroxyl group often does not match the number of the OH group (the above formula (It has been described in (32)), and there may be such a case, but any of R 31 and R 32 is a group defined in the following (vi) to (viii).
  • R 31 and / or R 32 forms a saturated and / or unsaturated condensed ring structure with ring A and the condensed ring is 6-membered or less
  • the carbon atom at the ⁇ -position is It may be tertiary or quaternary, and the ⁇ -position carbon is in the ⁇ -position (of the atoms forming the R 31 and R 32 , the atoms bonded to the aromatic ring of the ring A
  • the carbon atom at the ⁇ -position may be tertiary or quaternary.
  • (Iii) a group composed of a carbon atom, a hydrogen atom and an oxygen atom (for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group) Represents an ether group, provided that it is an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, or a group having no methine group at the terminal, and is in the ⁇ -position (the atoms forming R 31 and R 32 ).
  • an atom of an atom bonded to the aromatic ring of ring A) is a carbon atom or an oxygen atom, and in the case of a carbon atom, it is a primary or secondary carbon atom (that is, carbon of a methyl group, Represents the carbon forming the —CH 2 — bond).
  • the carbon atom at the ⁇ -position is tertiary Alternatively, it may be quaternary, and the carbon at the ⁇ -position is ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 31 and R 32 ). In the case where a double bond or a triple bond is formed with this atom, the carbon atom at the ⁇ -position may be tertiary or quaternary.
  • a halogen atom (V) a group composed of an atom selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom (however, an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, a terminal methine group) , NH 2 group, NH group, NOH group, SH group, SO 3 H group, and other groups containing active hydrogen such as SOH group, and the ⁇ -position (the atoms forming R 31 and R 32 )
  • the atom of the ring A bonded to the aromatic ring is a carbon atom, an oxygen atom or a sulfur atom, and in the case of a carbon atom, a primary or secondary carbon atom (that is, a methyl group) Carbon, which represents a carbon forming a —CH 2 — bond), and in the case of a sulfur atom, it is a
  • the carbon atom at the ⁇ -position is tertiary Alternatively, it may be quaternary, and the carbon at the ⁇ -position is ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 31 and R 32 ). In the case where a double bond or a triple bond is formed with this atom, the carbon atom at the ⁇ -position may be tertiary or quaternary.
  • (Vi) a group composed of a carbon atom and a hydrogen atom (which may further combine with ring A to form a ring structure), which is in the ⁇ position (forms R 31 and R 32) Of the atoms that are bonded to the aromatic ring of ring A) is a carbon atom, and the carbon atom is a tertiary or quaternary carbon atom (ie, forming a —CH— bond). Represents carbon that does not bond to hydrogen).
  • the condensed ring may be a 7-membered ring or more.
  • the ⁇ -position carbon forms a double bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 31 and R 32 ).
  • the ⁇ -position carbon may be a quaternary carbon, except that the ⁇ -position carbon forms a triple bond with the ⁇ -position atom.
  • (Vii) a group composed of a carbon atom, a hydrogen atom and an oxygen atom (for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group) Represents an ether group, provided that it is an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, or a group having no methine group at the terminal, and is in the ⁇ -position (the atoms forming R 31 and R 32 ).
  • the atom of the atom bonded to the aromatic ring of ring A) is a carbon atom.
  • the carbon atom is a tertiary or quaternary carbon atom (that is, a carbon that forms a —CH— bond or a carbon to which hydrogen does not bind), provided that R 31 and / or R 32 is a ring.
  • the condensed ring may be a seven-membered ring or more.
  • the ⁇ -position carbon forms a double bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 31 and R 32 ).
  • the ⁇ -position carbon may be a quaternary carbon, except that the ⁇ -position carbon forms a triple bond with the ⁇ -position atom.
  • a group composed of an atom selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom (however, an alcoholic OH group, a carbonyl group, an ester group, a carboxyl group, a terminal methine group) , NH 2 group, NH group, NOH group, SH group, SO 3 H group, and other groups containing active hydrogen such as SOH group, and the ⁇ -position (the atoms forming R 31 and R 32 )
  • the atom of the ring A bonded to the aromatic ring is a carbon atom or a nitrogen atom, and when it is a carbon atom, it is a tertiary or quaternary carbon atom (ie, a —CH—
  • the condensed ring may be a 7-membered ring or more.
  • the ⁇ -position carbon forms a double bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 31 and R 32 ).
  • the ⁇ -position carbon may be a quaternary carbon, except that the ⁇ -position carbon forms a triple bond with the ⁇ -position atom.
  • the nitrogen atom may be a tertiary nitrogen atom bonded to the ⁇ -position atom by a single bond.
  • the ring A contains at least one structure selected from the group consisting of a benzene ring, a naphthalene ring, and an anthracene ring is preferable.
  • the aromatic hydroxy compound and the isocyanate are separated by distillation, and the separated aromatic
  • the group hydroxy compound may be recycled as an aromatic hydroxy composition to be reacted with a compound having a ureido group.
  • the separation is selected according to the above-mentioned definition using the standard boiling point as an index.
  • the active aromatic hydroxy compound and the above active hydroxy compound are used as an aromatic hydroxy composition
  • the normal boiling point of the active aromatic hydroxy compound is inactive aromatic. If an aromatic hydroxy compound is selected so as to have a relationship higher by 10 ° C. or more than the standard boiling point of the hydroxy compound, it is easy to separate and purify both, but this is not essential.
  • the compound having the lowest standard boiling point among the active aromatic hydroxy compounds is the inactive aromatic hydroxy compound. Is selected so as to be higher by 10 ° C. or more than the compound having the highest standard boiling point.
  • the active and low activity aromatic hydroxy compounds are used in as few kinds as possible, and for example, it is preferable to use them one by one.
  • aromatic monohydroxy compounds that are easily available are preferred in view of industrial use.
  • aromatic monohydroxy compound represented by the following formula (40) is preferable.
  • R 35 , R 36 , and R 37 are groups independently selected from the above R 7 to R 14 groups (excluding aryl groups having a hydroxy group), and R 33 and R 34 groups are:
  • the aromatic hydroxy compound represented by the formula (40) is an aromatic monohydroxy compound having an integer of 6 to 50 carbon atoms, which is a group independently selected from the aforementioned R 31 and R 32 groups. . That is, the total carbon number of R 33 , R 34 , R 35 , R 36 and R 37 groups is an integer of 0 to 44.
  • R 33 and R 34 are each independently any one group defined by the following (i) to (ii).
  • (I) a group composed of a carbon atom and a hydrogen atom (which may further combine with ring A to form a ring structure), which is in the ⁇ -position (forms R 33 and R 34) Of the atoms that are bonded to the aromatic ring of ring A) is a carbon atom, and the carbon atom is a tertiary or quaternary carbon atom (ie, forming a —CH— bond). Represents carbon that does not bond to hydrogen).
  • the condensed ring may be a 7-membered ring or more.
  • the ⁇ -position carbon when the ⁇ -position carbon forms a double bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 33 and R 34 )
  • the ⁇ -position carbon may be a quaternary carbon, except that the ⁇ -position carbon forms a triple bond with the ⁇ -position atom.
  • a group composed of a carbon atom, a hydrogen atom and an oxygen atom for example, an ether group composed of an aliphatic group, an ether group composed of an aromatic group, or a group composed of an aliphatic group and an aromatic group
  • the atom of the atom bonded to the aromatic ring of ring A) is a carbon atom.
  • the carbon atom is a tertiary or quaternary carbon atom (that is, a carbon that forms a —CH— bond or a carbon that does not bond to hydrogen).
  • the condensed ring may be a 7-membered ring or more.
  • the ⁇ -position carbon when the ⁇ -position carbon forms a double bond with the atom at the ⁇ -position (next to the atom bonded to the aromatic ring of the ring A among the atoms forming the R 33 and R 34 )
  • the ⁇ -position carbon may be a quaternary carbon, except that the ⁇ -position carbon forms a triple bond with the ⁇ -position atom.
  • Preferred examples of the aromatic monohydroxy compound represented by the formula (40) include 2-tert-propylphenol (each isomer), 2-tert-butylphenol (each isomer), and 2-tert-pentyl. Phenol (each isomer), 2-tert-hexylphenol (each isomer), 2-tert-heptylphenol (each isomer), 2-tert-octylphenol (each isomer), 2-tert-nonylphenol (each isomer) ), 2-tert-decylphenol (each isomer), 2-tert-dodecylphenol (each isomer), 2-tert-octadecylphenol (each isomer), 2-sec-propylphenol (each isomer) 2-sec-butylphenol (each isomer), 2-sec-pentylphenol (each isomer), -Sec-hexylphenol (each isomer), 2-sec-h
  • R 33 , R 34 , R 35 , R 36 , R 37 group is a chain and / or cyclic saturated alkyl group, and at least of the R 33 and R 34 groups One is an aromatic monohydroxy compound in which the ⁇ -position carbon is a tertiary or quaternary carbon.
  • the carbonic acid derivative in the present embodiment refers to a compound represented by the following formula (19).
  • a composition for transporting and storing a compound having a ureido group is prepared by an N-substituted carbamic acid-O—R 2 ester production step, an N-substituted carbamic acid-O-aryl ester production step, ie, the step (R) described above.
  • the component used in Step (P) and Step (B) and recycled from the production step is used in the production of a compound having a ureido group
  • the composition for transporting and storing the compound having a ureido group It is a component that may be contained in the product. Further, it is a component that also serves as a raw material for a compound having a ureido group.
  • X and Y each represents an organic group having 1 to 50 carbon atoms or an amino group (—NH 2 ). However, X and Y are not amino groups at the same time. The number of carbon numbers represents an integer. )
  • Examples of the compound represented by the formula (19) used in the present embodiment include N-unsubstituted carbamic acid-O-aryl ester, N-unsubstituted carbamic acid-O—R 2 ester, and carbonate ester. .
  • N-unsubstituted carbamic acid As an explanation of the present embodiment and general formula names of the compounds, “N-unsubstituted carbamic acid”, “N-unsubstituted carbamic acid-O-aryl ester”, “N-unsubstituted carbamic acid-O—R 2 ester”
  • the N-unsubstituted carbamic acid is used in the sense that the NH 2 group of the carbamoyl group (NH 2 —CO—) is not substituted with a substituent. That is, the NH 2 group of the carbamoyl group (NH 2 —CO—) of N-unsubstituted carbamic acid is an NH 2 group.
  • N-unsubstituted carbamic acid-O—R 2 ester an N-unsubstituted carbamic acid-O—R 2 ester represented by the following formula (21) is preferably used.
  • the R 2 group is the same as the R 2 group of the alcohol represented by the formula (4), and is a group comprising an aliphatic group containing an integer carbon atom in the range of 1 to 14 or an aliphatic group to which an aromatic group is bonded.
  • the —O—R 2 group of the N-unsubstituted carbamic acid —O—R 2 ester represented by the formula (21) is the R 2 O group of R 2 OH of the alcohol represented by the formula (4) is there.
  • the N-unsubstituted carbamic acid-O—R 2 ester is an N-substituted carbamic acid —O— in the step (A) and / or step (R) using an alcohol (ie, using an alcohol).
  • N-unsubstituted carbamic acid-O—R 2 ester produced as a by-product in the production of the aryl ester or produced by a known method may be used.
  • the known method is preferably a reaction between isocyanic acid (HNCO) and alcohol as shown in the following reaction formula (22), and a method obtained from urea and alcohol as shown in the following reaction formula (23).
  • HNCO isocyanic acid
  • the N-unsubstituted carbamic acid-O—R 2 ester represented by the above formula (21) can be obtained.
  • the R 2 group the R 2 group mentioned in the description of the alcohol represented by the formula (4) can be preferably used.
  • Examples of such N-unsubstituted carbamic acid-O—R 2 ester represented by the formula (21) include methyl carbamate, ethyl carbamate, propyl carbamate (each isomer), butyl carbamate (each Isomers), pentyl carbamate (each isomer), hexyl carbamate (each isomer), heptyl carbamate (each isomer), octyl carbamate (each isomer), nonyl carbamate (each isomer), carbamine Decyl acid (each isomer), undecyl carbamate (each isomer), dodecyl carbamate (each isomer), tridecyl carbamate (each isomer), tetradecyl carbamate (each isomer), pentadecyl carb
  • a compound having a ureido group can be obtained from the above N-unsubstituted carbamic acid-O—R 2 ester by reacting with an organic primary amine by a known method.
  • the reaction formula is a reaction of the following formula (24).
  • the organic primary amine is represented by a monoamine structure, but it may be an organic polyprimary amine.
  • step (A) of reacting the organic primary amine and urea it is preferable to perform the step (A) of reacting the organic primary amine and urea to obtain a compound having a ureido group, but the above formula (24) may be simultaneously performed. Moreover, it is a preferable method because by-products can be used effectively.
  • N-unsubstituted carbamic acid-O-aryl ester an N-unsubstituted carbamic acid-O-aryl ester represented by the following formula (25) is preferably used.
  • Ar is a group derived from the aromatic hydroxy compound constituting the aromatic hydroxy composition
  • Ar—O— group is a hydroxyl group directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound. Represents a residue excluding a hydrogen atom.
  • the compound represented by the formula (25) is an N-substituted carbamic acid-O— in a process including any of the process (A), the process (P), and the process (B) using an aromatic hydroxy composition.
  • An N-unsubstituted carbamic acid-O-aryl ester produced as a by-product in the production of the aryl ester or produced by a known method may be used.
  • the known method is a reaction of isocyanic acid (HNCO) with an aromatic hydroxy compound as shown in the following reaction formula (26), or a method obtained from urea and an aromatic hydroxy compound as shown in the following reaction formula (27).
  • the aromatic hydroxy compound represented by the formula (2) is used as the aromatic hydroxy compound used at that time, whereby the N-unsubstituted carbamic acid-O-aryl ester represented by the above formula (25) is obtained. Obtainable.
  • Rings A and b are the same as the aromatic hydroxy compound represented by formula (2), and are included in the structure of the N-unsubstituted carbamic acid-O-aryl ester represented by formulas (26) and (27).
  • the oxygen-ring A bond bonded to the carbamoyl group (NH 2 —CO—) represents a residue obtained by removing a hydrogen atom from the hydroxy group bonded to the aromatic ring of the aromatic hydroxy compound.
  • a compound having a ureido group can be obtained by reacting with an organic primary amine by a known method.
  • the reaction formula is a reaction of the following formula (28).
  • both the N-unsubstituted carbamic acid-O-aryl ester and the organic primary amine are each represented by monovalent (meaning that there is one reaction site). It may be an acid-O-aryl ester or an organic polyprimary amine.
  • step (A) the reaction of the formula (24) derived from the above-mentioned N-unsubstituted carbamic acid-O—R 2 ester or the formula (28) derived from the N-unsubstituted carbamic acid-O-aryl ester ) May be carried out simultaneously.
  • the Ar group a structure in which one or more hydroxy groups bonded to the aromatic contained in the aromatic hydroxy compound mentioned in the description of the aromatic hydroxy compound represented by the formula (2) can be preferably used. That is, the —O—Ar group of the N-unsubstituted carbamic acid-O-aryl ester of the above formula (25) is directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound represented by the formula (2). A residue obtained by removing a hydrogen atom of a hydroxyl group can be preferably used.
  • the aromatic monohydroxy compound represented by the formula (31) or the formula (32) is preferable, and the active fragrance represented by the formula (38) is more preferable.
  • Group monohydroxy compounds Of course, one or more of them may be used.
  • Examples of such N-unsubstituted carbamic acid-O-aryl esters represented by the formula (21) include phenyl carbamate, carbamic acid (methylphenyl) (each isomer), carbamic acid (ethylphenyl) ( Isomers), carbamic acid (propylphenyl) (each isomer), carbamic acid (butylphenyl) (each isomer), carbamic acid (pentylphenyl) (each isomer), carbamic acid (hexylphenyl) (each isomer) ), Carbamic acid (heptylphenyl) (each isomer), carbamic acid (octylphenyl) (each isomer), carbamic acid (nonylphenyl) (each isomer), carbamic acid (decylphenyl) (each isomer) , Carbamic acid (biphenyl) (each isomer), carb
  • Preferable examples are N-unsubstituted carbamic acid-O-aryl esters in which the aryl group of the —O-aryl ester is a phenyl group substituted with an alkyl group or a phenyl group.
  • the N-unsubstituted carbamic acid-O— (R 2 or aryl) ester represented by the formula (21) or the formula (25) should be used effectively as a raw material for the synthesis of a compound having a ureido group.
  • the carbonic acid derivative in addition to the above-mentioned urea, alcohol, ammonia, N-substituted carbamic acid ester, carbonic acid ester described later, etc., a complicatedly substituted monomeric or multimeric urea compound, biuret, Nurate and the like may be contained, but such a compound may be contained.
  • N-unsubstituted carbamic acid-O— (R 2 or aryl) ester may be used, which means “N-substituted carbamic acid-O—R 2”. Ester or N-substituted carbamic acid-O-aryl ester ".
  • N-substituted carbamic acid-O-aryl ester produced by the method of the present embodiment is a compound represented by the following formula (43).
  • this embodiment will be described in detail later, a method of esterifying a compound having a ureido group and an aromatic hydroxy composition, an N-substitution by esterifying a compound having a ureido group and an alcohol.
  • the N-substituted carbamic acid-O-aryl ester represents an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring). More specifically, the O-aryl group in the carbamic acid-O-aryl ester group in the N-substituted carbamic acid-O-aryl ester is bonded to the aromatic ring carbon atom of the aromatic hydroxy compound.
  • the above-described method is a method in which a ureido group (—NHCONH 2 ) and an aromatic hydroxy compound are esterified to form a carbamic acid-O-aryl group (—NHCOOAr).
  • the group (—NHCONH 2 ) and an alcohol are esterified to form a carbamic acid —O—R 2 group (—NHCOOR 2 ), and then an ester exchange reaction with an aromatic hydroxy compound to form a carbamic acid —O—aryl group.
  • —NHCOOAr a ureido group
  • an aromatic hydroxy compound are esterified to form a carbamic acid-O-aryl group.
  • R 1 represents a group derived from a compound having an organic primary amine or ureido group as defined above
  • Ar is a group derived from the aromatic hydroxy compound represented by the formula (2) constituting the aromatic hydroxy composition, and the Ar—O— group is directly attached to the aromatic hydrocarbon ring from the aromatic hydroxy compound.
  • a and c are the values defined above.
  • the specific structure of the N-substituted carbamic acid-O-aryl ester represented by the above formula (43) is determined by the compound having an organic primary amine and / or ureido group and the aromatic hydroxy composition used.
  • a compound having a ureido group represented by formula (1) and / or an organic primary amine represented by formula (3) and an aromatic hydroxy compound represented by formula (2) as an aromatic hydroxy composition When used, an N-substituted carbamic acid-O-aryl ester represented by the following formula (44) is obtained, and the organic primary amine represented by the formula (5) and the aromatic hydroxy composition are represented by the formula (2).
  • a process including the step (C) a structure such as an N-substituted poly (carbamic acid-O-aryl ester) represented by the following formula (47) can be given.
  • N-substituted poly represents an N-substituted carbamic acid-O-alkyl ester having a plurality of carbamic acid-O-aryl ester groups in one molecule.
  • various N-substituted carbamic acid-O-aryl esters can be obtained by the production method in the present embodiment, and are represented by the above formula (43).
  • aryl means a monovalent aromatic ring in the Nomenclature rule defined by IUPAC, but because it could not find an appropriate name generically referring to the compounds in this embodiment, it is called “aryl”.
  • the group meaning the N-substituted carbamic acid-O-aryl ester of the present embodiment is the above-described N-substituted carbamic acid-O-aryl ester, or the N-substituted carbamic acid-O-aryl ester of the present embodiment.
  • Substituted carbamic acid-O-aryl ester may be replaced with N-substituted carbamic acid-O-Ar ester, that is, Ar has the above-mentioned meaning.
  • R 1 represents a group derived from an organic primary amine as defined above
  • Ring A is a group derived from the aromatic hydroxy compound constituting the aromatic hydroxy composition defined above, and among the hydroxyl groups directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound, Represents a residue with one hydrogen atom removed
  • the R 3 to R 14 groups represent the groups defined above; b, d, e, f, g, h, i, j, k, m, q are integers defined above, q is an integer of 1 to a or an integer of 1 to c. a and c are the values defined above.
  • a polyvalent aromatic hydroxy compound When a polyvalent aromatic hydroxy compound is used, a plurality of hydroxy groups on the aromatic group may react with a compound having different ureido groups, resulting in a high molecular weight and a complicated structure.
  • the N-substituted carbamic acid-O-aryl ester represented by the above formula (43) is usually obtained.
  • the manufacturing method in the present embodiment can be applied to a wide variety of compounds having a ureido group, organic primary amines, alcohols, and aromatic hydroxy compounds, and therefore cannot list all specific compounds.
  • N, N′-hexanediyl-di carboxylic acid
  • N, N′-hexanediyl-di carboxylic acid
  • N, N′-hexanediyl-di carbamic acid (methylphenyl) ester) (each isomer)
  • N, N′-hexane Diyl-di carbarbamic acid (ethylphenyl) ester) (each isomer
  • N, N′-hexanediyl-di carbarbamic acid (propylphenyl) ester) (each isomer)
  • N, N′-hexanediyl- Di carbamic acid (butylphenyl) ester) (each isomer)
  • Preferred N-substituted carbamic acid-O-aryl esters are N-substituted carbamic acid--obtained using the preferred compounds described in detail above for organic primary amines, aromatic hydroxy compounds, and compounds having a ureido group.
  • O-aryl ester for example, N obtained by reacting an active aromatic monohydroxy compound with an N-substituted aromatic organic monourea, N-substituted aromatic organic polyurea, or N-substituted aliphatic organic polyurea N-substituted carbamic acid-O-aryl ester, N-substituted carbamic acid-O-aryl ester obtained from active aromatic monohydroxy compound and N-substituted aromatic organic monourea condensed with a condensing agent Substituted carbamic acid-O-aryl ester.
  • the N-substituted carbamic acid-O—R 2 ester produced by the production method of the present embodiment is a compound represented by the following formula (49).
  • the present embodiment referred to here is a compound obtained when an N-substituted carbamic acid-O-aryl ester is produced in the step including the step (R) described in detail later.
  • a compound having a ureido group and an alcohol represented by the formula (4) are esterified to form a ureido group (—NHCONH 2 ) as a carbamic acid-O—R 2 ester group (—NHCOOR 2 ).
  • an N-substituted carbamic acid obtained by reacting a compound having at least one ureido group with an alcohol represented by the formula (4) in a liquid phase and extracting by-produced ammonia into the gas phase.
  • —O—R 2 ester which is an N-substituted carbamic acid —O—R 2 ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an R 2 group derived from an alcohol. Represents a carbamic acid ester.
  • OR 2 group in the carbamic acid-O—R 2 ester group (—NHCOOR 2 ) in the N-substituted carbamic acid-O—R 2 ester is bonded to the carbon atom of the alcohol. It is a residue obtained by removing a hydrogen atom from one hydroxy group (OH group).
  • R 1 represents a group derived from an organic primary amine as defined above
  • R 2 represents a group derived from an alcohol as defined above
  • r is an integer of 1 to a or an integer of 1 to c.
  • a and c are the values defined above.
  • N'-hexanediyl-di carbamic acid methyl ester
  • N, N'-hexanediyl-di carbamic acid ethyl ester
  • N, N'-hexanediyl-di carbarbamic acid propyl ester
  • N, N′-hexanediyl-di carbarbamic acid propyl ester
  • N, N′-hexanediyl-di carbarbamic acid butyl ester
  • N, N′-hexanediyl-di carbarbamic acid pentyl ester
  • N, N′-hexane Diyl-di carbarbamic acid hexyl ester
  • methylene-di cyclohexanedi (cyclohexane cyclohexanedi (cyclohexane cyclohexane
  • N-substituted carbamic acid-O—R 2 ester is N-substituted carbamic acid —O— obtained by using the preferred compounds described in detail in the above-mentioned organic primary amine, alcohol, and compound having a ureido group.
  • R 2 ester for example, N-substituted carbamic acid-O— obtained by reacting alcohol with N-substituted aromatic organic monourea, N-substituted aromatic organic polyurea, or N-substituted aliphatic organic polyurea.
  • R 2 ester is R 2 ester, alcohol and N- to N- substituted carbamic acid -O-R 2 ester obtained from a substituted aromatic organic mono urea condensed in condensing agent N- substituted carbamic acid -O-R 2 ester .
  • Carbonate is a component that is preferably contained in a specific amount in the composition for transfer and storage of the present embodiment.
  • Carbonic acid ester refers to a compound in which one or two atoms of two hydrogen atoms of carbonic acid; CO (OH) 2 are substituted with an aliphatic group or an aromatic group.
  • a compound represented by the following formula (20) is preferably used.
  • R 38 and R 39 are each independently a group selected from the above R 2 and Ar groups.
  • the above carbonate ester is a reaction of urea with alcohol and / or aromatic hydroxy compound, reaction of N-substituted carbamic acid-O- (R 2 or aryl) ester with alcohol and / or aromatic hydroxy compound, or formation It is formed by the disproportionation reaction of the carbonate ester.
  • R 2 and Ar groups are R 2 and Ar groups explained in N- substituted carbamate -O- (R 2 or aryl) ester.
  • Examples of the carbonate ester represented by the formula (20) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate (each isomer), dibutyl carbonate (each isomer), dipentyl carbonate (each isomer), and dihexyl carbonate.
  • each isomer diheptyl carbonate (each isomer), dioctyl carbonate (each isomer), dinonyl carbonate (each isomer), didecyl carbonate (each isomer), diundecyl carbonate (each isomer), didodecyl carbonate (each Isomers), ditridecyl carbonate (each isomer), ditetradecyl carbonate (each isomer), dipentadecyl carbonate (each isomer), dihexadecyl carbonate (each isomer), diheptadecyl carbonate (each isomer), dioctadecyl carbonate (each isomer) ), Dinonadecyl carbonate (each isomer), diphenyl carbonate, di (methylphenyl) carbonate (each isomer), di (ethylphenyl) carbonate (each isomer) ), Di (
  • the N-substituted carbamic acid-O-aryl ester is produced from the composition for transporting and storing a compound having a ureido group according to the present embodiment and the aromatic hydroxy compound and / or the ureido group.
  • a trace amount of carbonate ester is by-produced.
  • the N-substituted carbamic acid-O-aryl ester is produced, and further, the compound used in each step when the N-substituted carbamic acid-O-aryl ester is thermally decomposed to produce an isocyanate is recycled. Is a preferred embodiment.
  • the by-produced carbonic acid ester is a carbonic acid ester derived from an aromatic hydroxy compound and / or an alcohol used in producing the N-substituted carbamic acid-O-aryl ester, that is, R 38 of the above formula and R 38 with the addition of hydroxyl groups to R 39 OH, R 39 OH is a carbonic ester corresponding to the above-described aromatic hydroxy compound and / or alcohol.
  • N-substituted carbamic acid-O-aryl ester When an N-substituted carbamic acid-O-aryl ester is produced using the composition for transporting and storing a compound having a ureido group containing the carbonate ester, N-substituted carbamic acid-O— (R 2 or aryl) ester is condensed to a compound having an undesired ureylene group, and there is also a mechanism for regenerating an N-substituted carbamic acid-O- (R 2 or aryl) ester, which is a preferred embodiment. .
  • urea compounds, carbamates, and carbonates, complex or monomeric or multimeric urea compounds, biurets, nurate, and the like may be contained, but such compounds are contained. There is no problem.
  • the method for producing an N-substituted carbamic acid-O-aryl ester of this embodiment includes a compound having a ureido group represented by formula (1) and at least one aromatic hydroxy represented by formula (2).
  • N-substituted carbamic acid-O-aryl ester refers to an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring
  • N-substituted carbamic acid-O-aryl ester refers to an N-substituted carbamic acid ester in which an oxygen atom of a carbamic acid group (—NHCOO—) is bonded to an aromatic ring
  • the N-substituted carbamic acid-O-aryl ester comprising a step of esterifying the compound having a ureido group and at least one aromatic hydroxy composition represented by the formula (2).
  • a method for producing the N-substituted carbamic acid-O-aryl ester comprising a step of transesterifying the R 2 ester and the aromatic hydroxy composition.
  • a method for producing the N-substituted carbamic acid-O-aryl ester from the step including the step (B) from the compound having the ureido group and the aromatic hydroxy composition, or the ureido group The N-substituted carbamic acid-O-aryl ester is produced by a process comprising the step (R) and the step (P) from the compound having the compound, the aromatic hydroxy composition and the alcohol represented by the formula (4). is there.
  • the compound having the ureido group is a compound having a ureido group obtained in the step (A), and the above production methods include a production method and a step (A) each including the step (A) and the step (B).
  • N-substituted carbamic acid-O—R 2 ester is an N-substituted carbamic acid-O-ester derived from a compound having a ureido group and the R 2 group of the alcohol represented by the formula (4).
  • Step (D) Urea is recovered by performing the following step (D) before step (B) or step (R) or step (P) and / or simultaneously with step (B) or step (R) or step (P). .
  • the method for producing an N-substituted carbamic acid-O-aryl ester in the present embodiment includes the step (A) described above together with selection of a compound to be used such as an organic primary amine, an aromatic hydroxy composition, and additionally an alcohol.
  • a compound to be used such as an organic primary amine, an aromatic hydroxy composition, and additionally an alcohol.
  • Various N-substituted carbamic acid-O-aryl esters can be produced by selecting and combining the steps (G), and an isocyanate can be obtained from the N-substituted carbamic acid-O-aryl ester.
  • the compound having a ureido group used in the present embodiment may be a compound having a ureido group obtained by a known method.
  • it is a compound having a ureido group obtained in the following step (A).
  • FIG. (1) shows a conceptual diagram of the step (A) in the present embodiment.
  • the ureido reaction is a reaction in which the amino group of the organic primary amine is an ureido group, that is, a reaction in which the organic primary amine is converted into a compound having a ureido group.
  • reaction in which a compound having a ureido group is produced from an organic primary amine and urea is represented by the following formula (111), and proceeds while producing ammonia as a by-product, although not shown in the formula.
  • R represents an organic group substituted with two substituents.
  • reaction for producing a compound having a ureido group of the above formula (111) as a side reaction, for example, a compound having a ureylene group from a compound having a ureido group represented by the following formula (113) and an organic primary amine is used.
  • generate the compound which has a biuret group may occur simultaneously.
  • the reaction formula shown in the description of this embodiment is for showing the concept of the reaction (what the reactants and products are), and often does not describe a number indicating a stoichiometric ratio).
  • the amount of organic primary amine and urea that are raw materials used in the step (A) will be described.
  • the amount of urea used is in the range of 1 to 100 times the stoichiometric ratio to the amino group of the organic primary amine.
  • N-unsubstituted carbamic acid ester N-unsubstituted carbamic acid-O-R 2 ester and / or N-substituted carbamic acid-O-aryl ester can be used in the same manner as urea.
  • a compound having a ureido group can be obtained.
  • the amount of urea used above and below is the total stoichiometric amount of urea and N-unsubstituted carbamic acid-O-R 2 ester and N-unsubstituted carbamic acid-O-aryl ester. Value.
  • the amount of urea (and N-unsubstituted carbamic acid ester) used is small, a complicatedly substituted carbonyl compound or the like presumed to be derived from the above formula (113) is likely to be formed. Preference is given to using N-unsubstituted carbamic acid esters.
  • urea and N-unsubstituted carbamic acid ester (often N-unsubstituted carbamic acid-O—R 2 ester and / or N-unsubstituted carbamic acid-O present in an excessive amount in the reaction system of step (A) It is presumed that -aryl ester together with N-unsubstituted carbamic acid ester) has the effect of stabilizing the resulting compound having a ureido group.
  • a compound having a biuret bond for example, a compound on the right side of the following formula (125)
  • a compound having a biuret end in the process of producing the compound having the ureido group (Compound on the right side of the following formula (126)) may be produced.
  • the compound having an isocyanate terminal is a compound having a biuret bond by reaction with urea (and N-unsubstituted carbamic acid ester) (for example, the following formulas (125) and (126) will be described using urea). It is speculated that a compound having a biuret end may be produced.
  • the use of an excess amount of urea (and N-unsubstituted carbamic acid ester) is important for selectively producing a compound having a ureido group.
  • the amount of urea used is preferably in the range of 1 to 100 times, more preferably in the range of 1.1 to 10 times, and most preferably in the stoichiometric ratio with respect to the amino group of the organic primary amine. The range is 5 to 5 times.
  • the number of urea (and N-unsubstituted carbamic acid ester) molecules in the reaction system is always excessive with respect to the number of amino groups of the organic primary amine (a state in which the number is excessive if possible).
  • the total amount of urea (and N-unsubstituted carbamic acid ester) to be used is dissolved in a reaction solvent (details will be described later) to prepare a mixed solution, and an organic primary amine is added to the mixed solution.
  • the method is preferably practiced.
  • ammonia concentration in the system will be described. Note that the preferable range of the ammonia concentration described here is intended for the ammonia concentration in the reaction solution after a certain amount of a compound having a ureido group (for example, a yield of 5% or more with respect to the organic amine) is generated. The initial period is not covered.
  • the reaction that produces N-substituted carbamic acid —O— (R 2 and / or aryl) ester is an equilibrium reaction, and the equilibrium is largely biased toward the original system.
  • the reaction for producing a compound having a ureido group is a reaction in which the equilibrium is large and biased toward the production side, or an addition reverse reaction, It was found that the ammonia concentration in the system was almost independent. Such findings are unprecedented and surprising.
  • N-substituted carbamic acid ester is produced by the reaction of the compound having a ureido group and the aromatic hydroxy compound (above-mentioned) (Reaction of formula (118)) was found to be able to selectively produce a compound having a ureido group, and further, by holding ammonia to a certain degree or more, side reactions were suppressed and ureido with good selectivity. It has been found that a compound having a group can be obtained.
  • a preferable ammonia concentration that exhibits such an effect is higher than 10 ppm, more preferably higher than 100 ppm, still more preferably higher than 300 ppm, and most preferably higher than 1000 ppm.
  • N-substituted carbamic acid-O— (R 2 and / or aryl) ester is used, which means “N-substituted carbamic acid-O—R 2 ester”.
  • And / or N-substituted carbamic acid-O-aryl esters are examples of the carbamic acid-O— (R 2 and / or aryl) ester”.
  • R represents an organic group substituted with two substituents; R′OH represents a monovalent hydroxy compound (alcohol or aromatic hydroxy compound).
  • the reaction temperature in step (A) can be carried out in the range of 30 ° C to 250 ° C.
  • a high temperature is preferable, but on the other hand, an unfavorable reaction (for example, a decomposition reaction of a carbonic acid derivative, etc.) occurred at a high temperature, resulting in complicated substitution.
  • the temperature is more preferably 50 ° C. to 200 ° C., further preferably 70 ° C. to 180 ° C.
  • the reaction pressure varies depending on the type of compound used, the composition of the reaction system, the reaction temperature, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 kPa to 10 MPa (absolute pressure). In consideration of ease, a range of 0.1 kPa to 5 MPa (absolute pressure) is preferable.
  • the reaction time in step (A) retention time in the case of a continuous process
  • it is usually 0.001 to 100 hours, preferably 0.01 to 80 hours, more preferably 0.1 to 50 hours. .
  • Step (A) is a step of producing a compound having a ureido group.
  • Step (A) if there are many amino groups derived from unreacted organic amine, in the step (B) or the step (R) using the reaction solution at the time of storage when the composition for transfer and storage is used or after the step (A), a compound having a ureylene group is generated, In addition to a decrease in the amount of N-substituted carbamic acid-O-ester produced, there are many cases where adhesion to the reactor and solidification occur.
  • the step (A) it is preferable to produce a compound having a ureido group with a yield as high as possible and reduce the amount of amino groups derived from the organic primary amine.
  • the ratio of the number of amino groups derived from the organic primary amine to the number of ureido groups constituting the compound having a ureido group is preferably 0.25 or less, more preferably 0.1 or less, The reaction is preferably continued until 0.05 or less.
  • a catalyst can be used as necessary, for example, an organometallic compound such as tin, lead, copper, titanium, an inorganic metal compound, an alkali metal, an alkaline earth metal alcoholate, Basic catalysts such as lithium, sodium, potassium, calcium, barium methylate, ethylate, and butyrate (each isomer) can be used. If a catalyst is added, it is often necessary to remove the catalyst. Therefore, it is preferably carried out without adding a catalyst. When a catalyst is used, the catalyst may be removed after the reaction.
  • the N-substituted carbamic acid-O-aryl ester is thermally decomposed to obtain an isocyanate, which is separated or separated during the process of purifying the isocyanate. It is preferable to remove. If the isocyanate and the above catalyst are stored together, undesirable phenomena such as discoloration may occur.
  • a known method can be used as the removal method, and methods such as membrane separation, distillation separation, and crystallization can be preferably used.
  • a known method as described above can be preferably used as the removal method.
  • the reaction in the step (A) is preferably carried out in the liquid phase in the presence of a solvent from the viewpoint of reducing the viscosity of the reaction liquid and / or making the reaction liquid a uniform system.
  • a solvent examples include alkanes such as pentane (each isomer), hexane (each isomer), heptane (each isomer), octane (each isomer), nonane (each isomer), and decane (each isomer).
  • Aromatic hydrocarbons and alkyl-substituted aromatic hydrocarbons such as benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each isomer), naphthalene, etc .; acetonitrile, benzo Nitrile compounds such as nitriles; aromatics substituted by halogens or nitro groups such as chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer), chloronaphthalene, bromonaphthalene, nitrobenzene, nitronaphthalene, etc.
  • a hydroxy composition a composition containing an alcohol and / or an aromatic hydroxy compound
  • a hydroxy composition a hydroxy composition composed of one or more hydroxy compounds (alcohol represented by formula (4) and / or aromatic hydroxy compound represented by formula (2))
  • the hydroxy composition preferably used as the reaction solvent in A) is hereinafter referred to as “hydroxy composition a”). These solvents can be used alone or in a mixture of two or more.
  • the hydroxy compound constituting the hydroxy composition a is a hydroxy composition used in the step (B), or the step (R) or the step (P) (the aromatic hydroxy compound and / or the alcohol constituting the aromatic hydroxy composition). Or a part of the composition may be the same as or different from each other. However, since the operation is facilitated, the hydroxy composition a is used in the step (B). Or it is preferable that it is the same as the hydroxy composition used at a process (R), or is the composition which comprises this hydroxy composition.
  • the reaction in the step (A) is performed in the presence of an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the following formula (2)), or After the reaction in the step (A) is performed in the presence of an alcohol or an aromatic hydroxy composition, an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the following formula (2)) is used. ) Is more preferable. More preferably, the step (A) is carried out in the presence of an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the following formula (2)). When the step (R) is carried out after the step (A), only alcohol may be used. In that case, the aromatic hydroxy composition (at least one kind) is prepared after the reaction of the step (A).
  • an aromatic hydroxy composition a composition containing at least one aromatic hydroxy compound represented by the following formula (2)
  • the reaction solvent shown here can be used in any amount. However, when an alcohol is used as the reaction solvent, the stoichiometric ratio is more than 1 time with respect to the amino group of the organic primary amine. It can be used in a range less than 100 times. In order to improve the fluidity of the reaction liquid and allow the reaction to proceed efficiently, it is preferable to use an excess of alcohol relative to the amino group of the organic primary amine, but if too much alcohol is used, the reactor More preferably, the stoichiometric ratio is more than 5 times and less than 50 times, more preferably 8 times the amino group of the organic primary amine. More than 20 times less can be used.
  • an aromatic hydroxy composition as a reaction solvent in the step (A)
  • it is used in a stoichiometric ratio of more than 1 and less than 100 times with respect to the amino group of the organic primary amine. be able to.
  • the stoichiometric ratio is more than 2 times and less than 50 times, more preferably 3 times, with respect to the amino group of the organic primary amine. More than 20 times less can be used.
  • the solubility of the compound having a ureido group to be generated is considered.
  • Group hydroxy compounds are preferably used.
  • Japanese Patent Publication No. 2-48539 discloses that a compound having a ureido group is difficult to dissolve in n-butanol.
  • an aromatic hydroxy compound is a compound having a ureido group dissolved therein. It is often excellent in performance.
  • the aromatic hydroxy compound also has an effect of promoting the reaction between the organic primary amine and urea (and N-unsubstituted carbamic acid ester).
  • urea (and N-unsubstituted carbamic acid esters) have a large tendency to take an association state by hydrogen bonding, but aromatic hydroxy compounds are acidic. Having a hydroxy group, the hydroxy group suppresses association between urea (and N-unsubstituted carbamic acid ester), and reacts with urea (and N-unsubstituted carbamic acid ester) (urea (and N-unsubstituted)
  • the present inventors presume that this may be to facilitate the access of the amine to the carbon constituting the carbonyl group of the carbamate ester).
  • the aromatic hydroxy compound When using an aromatic hydroxy composition as a reaction solvent, the aromatic hydroxy compound may be used alone or mixed with other solvents, but the amount of aromatic hydroxy compound used is Use within the above range of values. Even when an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by the following formula (2)) is added after performing the step (A) in the presence of alcohol, An aromatic hydroxy composition is used in the above range. At that time, the amount of alcohol used in the reaction in the step (A) is also the stoichiometric ratio of the alcohol represented by the aromatic hydroxy compound described above with respect to the organic primary amine. When water is used in step (A), it is preferably used with an aromatic hydroxy composition and / or alcohol.
  • the compound having a ureido group obtained in the step (A) is used to form a composition for transporting and storing having a ureido group, the amount of the aromatic hydroxy compound described above is added to form an aqueous phase and an organic phase. Or an aromatic hydroxy compound or a compound having a ureido group may solidify. Further, when the step (A) is added, the amount of the aromatic hydroxy compound described above is added, and when the step (R) or the step (B) is performed, a uniform liquid cannot be fed for the above reasons, The pump or piping may be clogged.
  • water is removed before or after the aromatic hydroxy compound is added.
  • the amount to be removed depends on the compound and composition to be used, but in the reaction solution (or mixed solution) after removal, it is in the range of 10 ppm to 10 wt%, preferably 10 ppm to 5%, more preferably 10 ppm to 2%. Remove until As a method of removing, a known method of removing water can be used.
  • a method of distilling off under reduced pressure or normal pressure a method using an adsorbent such as zeolite, a method of adding a hydrolyzable compound such as acetal and removing it by a hydrolysis reaction, water such as N, N-dicyclohexylcarbodiimide
  • water such as N, N-dicyclohexylcarbodiimide
  • the method of removing with a compound that reacts with can be preferably used. More preferred is a method by distillation.
  • the water content in the reaction is 10 ppm to 10 wt%, preferably 10 ppm to 5%, more preferably 10 ppm. Use in the range of ⁇ 2%.
  • the present inventors have found that the reaction rate of the step (A) is surprisingly improved by the presence of water. Therefore, it is a preferable method that water coexists during the reaction. Although the details of this effect have not been elucidated, it is presumed that the effect of increasing the nucleophilicity of the organic primary amine may be expressed by water.
  • a well-known reactor can be used.
  • conventionally known reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination.
  • a tank reactor equipped with a stirrer is preferable.
  • the material of the reactor is not particularly limited, and a known material can be used.
  • glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used.
  • SUS304, SUS316, SUS316L, etc. are also inexpensive and can be used preferably.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary. For example, a step of removing generated ammonia, a step of purifying an organic primary amine, a step of dissolving urea in an aromatic hydroxy compound, a step of dissolving an aromatic hydroxy compound, a step of separating alcohol, an aromatic hydroxy compound Processes and equipment in a range that can be envisaged by the contractor and the engineer, such as separation and / or purification, purification of compounds having a ureido group from the produced reaction solution, incineration and disposal of by-products, etc. You can add it. *
  • reaction solvent when adjusting the composition for transporting and storing the compound having a ureido group to a desired composition, before performing the step (B) or the step (R), the step The reaction solvent may be removed from the reaction solution of (A), or the above adjustments and steps may be performed without removal.
  • the hydroxy compound used as the reaction solvent in step (A) is preferably used as it is as part of the hydroxy composition in step (B) or step (R).
  • Ammonia produced as a by-product in the step (A) is introduced into the condenser provided in the reactor under reduced pressure or normal pressure, and is derived from urea, part or all of the hydroxy composition used in the step (A).
  • the compound having a carbonyl group may be condensed to recover ammonia as a gas.
  • an aromatic hydroxy compound containing a compound having a ureido group (specifically, a compound having an N-substituted ureido group) and at least one aromatic hydroxy compound represented by the formula (2)
  • the ureido By performing an esterification reaction, or an esterification reaction and a transesterification reaction (ie, including step (B), or step (R) and step (P)) from the composition, the ureido And a compound having a group and at least one N-substituted carbamic acid-O-aryl ester derived from the aromatic hydroxy composition (the N-substituted carbamic acid-O-aryl ester is a carbamic acid group (- NHCOO-) represents an N-substituted carbamic acid ester in which the oxygen atom is bonded to an aromatic ring).
  • a method of performing include five aspects described below.
  • other modes may be possible based on the present embodiment, and there is no limitation of the following five
  • Route 1 Method of performing step (B) Route 2) Method of performing step (B) and performing step (C) Route 3) Method of performing step (R) and performing step (P) Route 4) Process (R) ), Performing the step (P), and performing the step (C). Route 5) performing the step (R), performing the step (C), and performing the step (P).
  • the compound having an ureido group (or a reaction solution containing a compound having a ureido group) and an aromatic hydroxy composition are esterified to produce an N-substituted carbamic acid-O—.
  • a method for obtaining an aryl ester which includes a step (R), is obtained by esterifying a compound having a ureido group and an alcohol to obtain an N-substituted carbamic acid-O—R 2 ester, and then the step (P).
  • the N-substituted carbamic acid-O—R 2 ester and the aromatic hydroxy composition are transesterified to obtain an N-substituted carbamic acid-O-aryl ester.
  • Any of the above methods is a method for producing an N-substituted carbamic acid-O-aryl ester from a compound having a ureido group (after being obtained) and an aromatic hydroxy composition.
  • Route 1) is a method of performing step (B). This is a method for producing an N-substituted carbamic acid-O-aryl ester by reacting a compound having a ureido group with an aromatic hydroxy composition or from a composition for transferring and storing a compound having a ureido group.
  • Step (B) Step (B): reacting a compound having at least one ureido group with an aromatic hydroxy composition (a composition containing at least one aromatic hydroxy compound represented by formula (2)) in a liquid phase And extracting the by-produced ammonia into the gas phase to obtain an N-substituted carbamic acid-O-aryl ester. (This reaction is an esterification reaction.)
  • the compound having at least one ureido group may be a compound having a ureido group produced by a known method as long as it is a compound having a ureido group represented by the formula (1).
  • it is a reaction liquid containing the compound having at least one ureido group produced in the step (A) and the compound having at least one ureido group produced in the step (A).
  • the reaction liquid is a liquid after completion of the reaction in step (A) and / or the reaction in step (A) in the presence of an alcohol or an aromatic hydroxy composition, and then an aromatic hydroxy composition (at least one kind of The liquid which added the composition containing the aromatic hydroxy compound represented by following formula (2) is pointed out, and the reaction liquid containing the compound and hydroxy composition which have at least 1 sort (s) of ureido group is represented.
  • the composition for transferring and storing a compound having a ureido group described above may be used in place of the reaction solution containing the compound having at least one ureido group produced in the above step (A).
  • the method is also one aspect of the present embodiment.
  • Step (B) is a step of producing an N-substituted carbamic acid-O-aryl ester by esterifying the compound having a ureido group obtained in step (A) with an aromatic hydroxy composition. This is a preferred embodiment.
  • FIG. 2 is a conceptual diagram showing the step (B).
  • the organic primary amine used in this route is the organic primary amine represented by the formula (3), and the compound having a ureido group obtained in the step (A) of this route is derived from the organic primary amine.
  • a compound having a ureido group represented by formula (1), and the N-substituted carbamic acid-O-aryl ester obtained in step (B) of this route is represented by the formula (43 N-substituted carbamic acid-O-aryl ester represented by Examples of each specific compound are included in the above-described compounds.
  • the hydroxy composition a used as the reaction solvent in the step (A) includes the hydroxy composition of the step (B) (that is, the aromatic hydroxy composition used in the step (B)).
  • the reaction solution obtained in the step (A) is used as it is.
  • (B) can be performed.
  • the hydroxy composition a used as the reaction solvent in the step (A) is different from the hydroxy composition in the step (B)
  • a hydroxy compound is newly added to the reaction solution obtained in the step (A).
  • Step (B) may be carried out, or one or more hydroxy compounds are newly added to the reaction solution obtained in Step (A), and subsequently used as a reaction solvent in Step (A).
  • Step (B) may be carried out after separating part or all of the hydroxy composition, or after removing part or all of the hydroxy composition used as the reaction solvent in step (A), You may perform a process (B), after adding the 1 type or multiple types of hydroxy compound.
  • the newly added hydroxy compound is an aromatic hydroxy composition containing at least one aromatic hydroxy compound represented by the above formula (2).
  • the aromatic hydroxy composition used in step (B) is preferably an aromatic hydroxy composition containing an aromatic hydroxy compound represented by formula (7) or formula (31), more preferably active.
  • step (B) is carried out using an aromatic hydroxy composition containing formula (32), more preferably formula (38).
  • a method for producing an N-substituted carbamic acid-O-alkyl ester by reacting with an alcohol using a compound having a ureido group is disclosed in JP-A-6-41045.
  • the N-substituted carbamic acid-O-alkyl ester is easily heat-denatured and easily produces a compound having a ureylene group. Further, if an isocyanate is produced by thermally decomposing the N-substituted carbamic acid-O-alkyl ester, the thermal decomposition temperature becomes high and the reverse reaction of the thermal decomposition reaction tends to occur.
  • N-substituted carbamic acid-O-aryl ester is obtained by reacting a compound having a ureido group with an aromatic hydroxy compound, N-substituted carbamic acid-O-aryl ester is reduced with little heat denaturation. It has been found that -substituted carbamic acid-O-aryl esters can be obtained.
  • the method for separating the reaction solvent used in the step (A) is not particularly limited, and known methods such as distillation separation, membrane separation, and extraction separation can be used, but distillation separation is preferable.
  • distillation separation is preferable.
  • N-substituted carbamic acid-O-alkyl esters are often easily heat-denatured.
  • step (A) even if an alcohol is used in step (A) and a small amount of N-substituted carbamic acid-O—R 2 ester is produced in step (B), the aromatic hydroxy composition is present. Then, it discovered that this modification
  • step (B) When the step (B) is carried out in the presence of an alcohol, a slight amount of N-substituted carbamic acid-O—R 2 ester may be produced together with the N-substituted carbamic acid-O-aryl ester. ) It is preferable to remove alcohol before carrying out or to carry out while removing alcohol at the same time as carrying out step (B). Since N-substituted carbamic acid-O—R 2 ester is a compound having a higher thermal decomposition temperature at the time of performing step (F) than N-substituted carbamic acid-O-aryl ester, step (B) is preferably used.
  • step (A) no alcohol is used in step (A) (ie, no alcohol is used throughout the process) and N-substituted carbamic acid-O—R 2 esters are formed. It is preferable to reduce the amount.
  • the reaction conditions for producing the N-substituted carbamic acid-O-aryl ester by the reaction of the compound having a ureido group and the aromatic hydroxy composition in step (B) vary depending on the compound to be reacted, but the aromatic used
  • the amount of the aromatic hydroxy compound in the hydroxy composition is in the range of 1 to 500 times the stoichiometric ratio with respect to the ureido group of the compound having a ureido group to be used. When the amount is less than 1 time, a complex substituted carbonyl compound or a high molecular weight compound having a carbonyl bond in the molecule is likely to be formed. Therefore, it is preferable to use a large excess of aromatic hydroxy compound.
  • the reaction temperature depends on the compound used, but is preferably in the range of 100 ° C to 350 ° C. A temperature lower than 100 ° C. is not preferable because the reaction is slow, the reaction hardly occurs, or the number of complicatedly substituted carbonyl compounds increases. On the other hand, at a temperature higher than 350 ° C., urea (and N-unsubstituted carbamic acid ester) remaining in the step (A) or formed in the system of the step (B) is decomposed or the hydroxy composition is dehydrated.
  • a more preferable temperature is in the range of 120 ° C. to 320 ° C., more preferably in the range of 140 ° C. to 300 ° C.
  • the reaction for producing the N-substituted carbamic acid-O-aryl ester is an equilibrium reaction, and since the reaction is biased toward the original system, the by-product ammonia is removed from the system as much as possible. It is preferable to carry out the reaction.
  • ammonia is removed so that the ammonia concentration in the reaction solution is 1000 ppm or less, more preferably 300 ppm or less, further preferably 100 ppm or less, and most preferably 30 ppm or less (in the reaction solution, the step (B ) Means in the liquid phase at the time of implementation).
  • a reactive distillation method a method using an inert gas, a membrane separation, a method using adsorption separation, and the like can be performed.
  • the reactive distillation method is a method in which ammonia that is sequentially generated under the reaction is separated in a gaseous state by distillation.
  • the method using an inert gas is a method in which ammonia that is sequentially generated under reaction is separated from a reaction system by being accompanied by an inert gas in a gaseous state.
  • the inert gas for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane or the like is used alone or in combination, and the inert gas is preferably introduced into the reaction system.
  • Examples of the adsorbent used in the adsorption separation method include adsorbents that can be used under temperature conditions in which the reaction is performed, such as silica, alumina, various zeolites, and diatomaceous earth.
  • the method for removing these ammonia out of the system may be carried out alone or in combination of a plurality of methods.
  • a catalyst can be used for the purpose of increasing the reaction rate.
  • catalysts include basic catalysts such as lithium, sodium, potassium, calcium, barium methylate, ethylate, butyrate (isomers), rare earth elements, antimony, bismuth, and oxides of these elements. , Sulfides and salts, simple boron and boron compounds, copper group, zinc group, aluminum group, carbon group, titanium group metals and their metal oxides and sulfides in the periodic table, carbon other than carbon in the periodic table Group, titanium, vanadium, and chromium group carbides and nitrides are preferably used.
  • the amount used is not particularly limited, but the catalyst can be used in a stoichiometric ratio of 0.0001 to 100 times the ureido group of the compound having a ureido group. If a catalyst is added, it is often necessary to remove the catalyst. Therefore, it is preferably carried out without adding a catalyst.
  • the reaction pressure varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 Pa to 10 MPa (absolute pressure), which facilitates industrial implementation.
  • the range of 0.1 Pa to 5 MPa (absolute pressure) is more preferable, and in view of removing gaseous ammonia out of the system, 0.1 Pa to 1.5 MPa (absolute pressure) is more preferable.
  • the reaction time (residence time in the case of continuous reaction) varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, the reaction pressure, etc., but is usually from 0.01 to 100 hours.
  • the reaction time can also be determined by the amount of N-substituted carbamic acid-O-aryl ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) as the target compound.
  • the reaction solution is sampled to quantify the content of N-substituted carbamic acid-O-aryl ester (in some cases, the total with N-substituted carbamic acid-O—R 2 ester).
  • the reaction may be stopped after confirming that the compound having a ureido group is produced in a yield of 10% or more, or the reaction may be conducted after confirming that the yield is 90% or more. You may stop.
  • the reaction liquid containing the N-substituted carbamic acid-O-aryl ester in the step (B) is subjected to a thermal decomposition reaction in the step (F) to obtain an isocyanate.
  • the yield is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more.
  • reaction solvent for example, pentane (each isomer), hexane (each isomer), heptane (each isomer) ), Octane (each isomer), nonane (each isomer), decane (each isomer), and other alkanes; benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (Each isomer), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; nitrile compounds such as acetonitrile and benzonitrile; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer) Body),
  • aromatic compounds substituted by nitro groups polycyclic hydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, dibenzyltoluene (each isomer); cyclohexane, cyclopentane, cyclooctane, ethyl Aliphatic hydrocarbons such as cyclohexane; Ketones such as methyl ethyl ketone and acetophenone; Esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, and benzyl butyl phthalate; Tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether , Ethers such as diphenyl sulfide and thioethers; ketone compounds such as acetone and methyl ethyl ketone; ester
  • the reaction includes a hydroxy composition and a compound having a carbonyl group derived from urea (N-unsubstituted carbamic acid ester, biuret, etc., a compound that inherits the carbonyl group that urea had, And a gas phase containing ammonia by-produced in the reaction and a liquid phase in which the reaction is carried out. Most of the reactions are performed in the liquid phase, but depending on the reaction conditions, the reactions may occur in the gas phase. At that time, the liquid phase volume content in the reactor in which the reaction is carried out is preferably 50% or less.
  • a polymer by-product When the reaction is carried out continuously over a long period of time, a polymer by-product may be generated due to fluctuations in operating conditions (temperature, pressure, etc.), but if the liquid phase volume content in the reactor is large, Such polymeric by-products can be prevented from adhering to and accumulating in the reactor. However, if the liquid volume content is too large, the removal efficiency of by-product ammonia may deteriorate and the yield of N-substituted carbamic acid-O-aryl ester may be reduced.
  • the content is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less (in the case of a tank reactor, the liquid phase volume content refers to the reaction tank section and the tower reactor).
  • the stage below the feed stage (not including the bottom of the column and the reboiler part), and in the case of a thin film distiller, the ratio of liquid phase capacity to the capacity of the thin film distiller is represented.
  • the reaction apparatus used for carrying out the reaction is not particularly limited, and a known reactor can be used, but a tank-type and / or tower-type reactor is preferably used. A reactor equipped with a condenser is preferred.
  • the reaction is a system including a gas phase containing a hydroxy composition, a compound having a carbonyl group derived from urea, and ammonia by-produced in the reaction, and a liquid phase for performing the reaction.
  • the liquid phase volume content in the reactor in which the reaction is performed is preferably 50% or less, and the reactor that performs the reaction is also selected to meet the conditions.
  • conventionally known reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination.
  • a well-known condenser can be used.
  • conventionally known condensers such as a multi-tube cylindrical condenser, a double-pipe condenser, a single-pipe condenser, and an air-cooled condenser can be used in appropriate combination.
  • the condenser may be provided inside the reactor, or may be provided outside the reactor and connected to the reactor by piping.
  • the type of the reactor or condenser, the condensate Considering the handling method, etc., various forms are adopted.
  • the material of the reactor and the condenser and known materials can be used.
  • glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used.
  • SUS304, SUS316, SUS316L, etc. are also inexpensive and can be preferably used. If necessary, instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added. A known method such as cooling water or brine can be used. A process may be added as necessary.
  • a step of dissolving a compound having a ureido group in an aromatic hydroxy composition a step of dissolving an aromatic hydroxy compound, a step of separating alcohol, a step of separating and / or purifying an aromatic hydroxy compound, and a generated reaction solution
  • a process for purifying N-substituted carbamic acid-O-aryl esters from the above, a process for incineration and disposal of by-products and the like may be added.
  • a compound having a ureido group and an aromatic hydroxy composition are reacted in a liquid phase using a reactor (comprising a condenser) to obtain an N-substituted carbamic acid-O-aryl ester.
  • a reactor comprising a condenser
  • the gaseous component containing the compound having a carbonyl group derived from urea and ammonia produced as a by-product in the reaction, which is produced in the step (B) is introduced into the condenser provided in the reactor.
  • a part or all of the aromatic hydroxy composition and a compound having a carbonyl group derived from urea are condensed, and ammonia is recovered as a gas.
  • the compound having a carbonyl group derived from urea contained in ammonia recovered as a gas from the condenser is set to a specific amount or less. That is, the ratio of the number of carbonyl groups (—C ( ⁇ O) —) contained in the ammonia-containing compound having a carbonyl group derived from urea to the ammonia molecule is 1 or less, preferably 0.8. 5 or less, more preferably 0.1 or less, and still more preferably 0.01 or less.
  • the reason why the amount of the compound having a carbonyl group derived from urea contained in the ammonia is in a specific range is to avoid adhesion and accumulation of solid components in a line for transferring the ammonia from the condenser. It is.
  • solid components adhering and accumulating in the ammonia transfer line can be identified, as a result of studies by the present inventors, it has been found that most of them are compounds having a carbonyl group.
  • a method of avoiding such adhesion and accumulation of solid components a method of decomposing a compound having a carbonyl group by heating a line for transferring ammonia can be considered, but in the study by the present inventors, only heating is performed.
  • decomposition products for example, isocyanic acid
  • the decomposition products react with compounds having other carbonyl groups, so that the adhesion and accumulation of solid components can be completely avoided. was difficult.
  • the compound having a carbonyl group contained in the ammonia or a decomposition product thereof is rapidly generated particularly at the outlet of the line for transferring ammonia (a portion in contact with the atmosphere). It turned out to be solidified by cooling, and the adhesion and accumulation of solid components were often significant.
  • the present inventors have surprisingly found that the compound having a carbonyl group derived from a carbonic acid derivative contained in the ammonia is not more than the specific amount described above, so that a solid is obtained. It has been found that the problem of component adhesion and accumulation can be solved.
  • the present inventors have a compound having a carbonyl group derived from a carbonic acid derivative or a carbonyl group derived from the carbonic acid derivative for adhesion or accumulation to a line. It is assumed that it is caused by the decomposition and / or polymerization product of the compound, and by making the carbonyl group contained in the compound having a carbonyl group derived from the carbonic acid derivative below a specific concentration, the carbonyl derived from the carbonic acid derivative This is considered to be because the adhesion of the group-containing compound itself and the decomposition and / or polymerization reaction rate of the compound are remarkably reduced.
  • the condensed aromatic hydroxy composition and the compound having a carbonyl group derived from urea are converted into the compound having the carbonyl group derived from the condensed urea hydroxy composition.
  • the stoichiometric ratio is 1 or more, preferably the stoichiometric ratio is 2 or more, more preferably the stoichiometric ratio is 3 or more. The reason for this range is that the mixture of the aromatic hydroxy composition and the compound having a carbonyl group derived from urea that is condensed in the condenser can be made into a uniform liquid mixture. This not only facilitates handling of the mixture, but also avoids problems such as adhesion and accumulation of solid components on the condenser.
  • the mixture of the aromatic hydroxy composition and the compound having a carbonyl group derived from urea condensed in the condenser in the step (B) is circulated inside the reactor, and the step (A). It may be reused in the reaction.
  • the amount of ammonia contained in the mixture is preferably 5000 ppm or less, more preferably 3000 ppm or less, and still more preferably 2000 ppm or less.
  • various compounds are recovered as compounds having a carbonyl group derived from urea, but there is no particular limitation on the reuse of these compounds.
  • Route 2) is a method of performing step (B) and performing step (C). Route 2) is also an aspect of the method shown in route 1).
  • the organic primary amine is an aromatic organic monoprimary amine represented by the following formula (5)
  • the following step (C) is carried out, From the N-substituted carbamic acid-O-aryl ester obtained in B), at least two molecules of the N-substituted carbamic acid-O-aryl ester are bridged with a methylene group (—CH 2 —).
  • This is a method for obtaining an acid-O-aryl ester.
  • the aromatic hydroxy compound constituting the aromatic hydroxy composition used in step (A) and / or step (B) uses an aromatic monohydroxy compound.
  • At least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are obtained by crosslinking an aromatic group derived from an aromatic organic monoprimary amine contained in the ester with a methylene group (—CH 2 —).
  • the present root 2) N- substituted carbamic acid -O-R 2 ester in step (A) and / or step (B) by-produced when using alcohol N- substituted carbamic acid -O-R 2 The ester is shown.
  • This route uses the organic primary amine whose organic primary amine is represented by the following formula, performs the step (A) to obtain a compound having a ureido group derived from the organic primary amine, and then the step ( B) to obtain an N-substituted carbamic acid-O-aryl ester derived from the compound having the ureido group, and then step (C) is carried out.
  • the organic primary amine used in this route is the organic primary amine represented by the formula (5)
  • the compound having a ureido group obtained in the step (A) of this route is the organic primary amine.
  • the substituted carbamic acid-O-aryl ester is an N-substituted carbamic acid-O-aryl ester represented by the formula (43) derived from the compound having the ureido group, and more specifically, the following formula (149) N-substituted carbamic acid-O-aryl ester represented by Examples of each specific compound are included in the above-described compounds.
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring a substituted to group at any position to keep the ring from R 3 may be substituted an aromatic ring each independently R 6 groups, also with an aromatic ring from R 3 by bonding R 6 originally between R 3 to R 6 groups may be hydrogen atoms or groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aryl groups having hydroxy groups, saturated aliphatic bonds and / or An aromatic group represented by the formula (5), which is a group selected from a group composed of ether-bonded groups, wherein R 3 to R 6 have an integer of 0 to 7 carbon atoms.
  • the total number of carbon atoms constituting the organic mono primary amine is 6 to 1 It consists of an integer number of.
  • the compound having a ureido group obtained in the step (A) is a compound having at least one ureido group represented by the following formula (148).
  • R 3, R 4, R 5 , R 6 groups of formula (148) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5)
  • a compound in which the amino group (—NH 2 group) of the organic primary amine represented by the formula (5) is a ureido group (—NH—CO—NH 2 ).
  • At least one position of the ortho-position and / or para-position of the ureido group of the N-substituted aromatic organic monourea represented by the formula (148) is unsubstituted, and the R 3 to R 6 groups each have aromaticity of the ring R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with the aromatic ring.
  • the R 3 to R 6 groups may be formed of a hydrogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aryl group having a hydroxy group, a saturated aliphatic bond and / or an ether
  • a group selected from the group consisting of a bond and a group of R 3 to R 6 is a group having an integer in the range of 0 to 7 carbon atoms, and is an N-substituted group represented by formula (148)
  • Ureido group constituting aromatic organic monourea The total carbon number excluding (—NH—CO—NH 2 ) is composed of 6 to 13. )
  • the N-substituted carbamic acid-O-aryl ester obtained in the step (B) is at least one N-substituted carbamic acid-O-aryl ester represented by the following formula (149).
  • R 3, R 4, R 5 , R 6 groups of formula (149) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5)
  • a ureido group (—NH—CO—NH 2 ) of a compound having a ureido group represented by formula (148) is a carbamic acid-O-aryl ester group.
  • R 3 to R 6 groups are the groups indicated above.
  • the organic primary amine to be used is the formula (5), and the steps (A) and (B) of this route are the steps (A) and steps of the route 1. It implements on the conditions of (B).
  • step (C) at least one N-substituted carbamic acid-O-aryl ester (containing a reaction solution) obtained in the step (B) is crosslinked with a methylene group (—CH 2 —), and at least two molecules of the N- substituted carbamic acid -O- (R 2 or aryl) ester methylene group (-CH 2 -) crosslinked with, is to obtain a N- substituted carbamate -O- (R 2 or aryl) ester .
  • step (C) at least one molecule of the N-substituted carbamic acid-O-aryl ester represented by the following formula (150) was crosslinked with the methylene group (—CH 2 —).
  • N-substituted carbamic acid-O-aryl ester is obtained.
  • a polyvalent aromatic hydroxy compound may be used, but in that case, crosslinking may occur at a place other than desired.
  • the aromatic hydroxy compound represented by the formula (31) is preferable, more preferably an active aromatic hydroxy compound represented by the formula (38) is used, and more preferably, Among the active aromatic hydroxy compounds represented by the formula (38), the aromatic monohydroxy compounds in which the R 26 and R 27 groups are hydrogen atoms and the other substituents are chain and / or cyclic saturated alkyl groups.
  • the aromatic monohydroxy compounds in which the R 26 and R 27 groups are hydrogen atoms and the other substituents are chain and / or cyclic saturated alkyl groups.
  • the aromatic monohydroxy compounds in which the R 26 and R 27 groups are hydrogen atoms and the other substituents are chain and / or cyclic saturated alkyl groups.
  • the aromatic monohydroxy compounds in which the R 26 and R 27 groups are hydrogen atoms and the other substituents are chain and / or cyclic saturated alkyl groups.
  • Ring A is a group derived from an aromatic hydroxy compound constituting the aromatic hydroxy composition as defined above, and is a group of hydroxyl groups directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound. Represents a residue with one hydrogen atom removed,
  • the R 3 to R 6 groups represent the groups defined above; m is an integer of 0 to 6.
  • the N-substituted carbamic acid-O-mono (aryl ester) represented by the above formula (149) can be directly subjected to a thermal decomposition reaction to produce a monoisocyanate.
  • the isocyanate is preferably a polyfunctional isocyanate. Therefore, there is a method of obtaining a polyfunctional isocyanate by subjecting the N-substituted carbamic acid mono (aryl ester) to a multimer in advance by the above step (C) and then subjecting the multimer to a thermal decomposition reaction. Can be done.
  • N-substituted carbamic acid-O-mono represents an N-substituted carbamic acid-O-aryl ester having one carbamic acid-O-aryl ester group in the molecule.
  • step (C) the N-substituted carbamic acid-O-aryl ester obtained in step (B) of route 2) is often referred to as N-substituted carbamic acid-O-mono (aryl ester) or N-substituted carbamic acid monoaryl ester.
  • the step (C) can be carried out by a known method (for example, refer to German Patent No. 1042891).
  • the aromatic hydroxy composition used in step (B) is separated from the resulting reaction solution containing the N-substituted carbamic acid-O-aryl ester.
  • the step (C) may be performed in the presence of an aromatic hydroxy compound
  • the aromatic hydroxy compound may also be cross-linked with a methyleneated cross-linking agent to produce a by-product such as a polyaromatic hydroxy compound.
  • the amount of the methyleneated cross-linking agent used may be increased, so that the aromatic hydroxy compound is preferably separated.
  • the separation method may be a known method, and varies depending on the compound to be used. However, the separation method is a method using distillation or extraction and separation using the difference in solubility between the N-substituted carbamic acid-O-aryl ester and the aromatic hydroxy compound.
  • the amount of the aromatic hydroxy compound after the separation operation is 1 times or less, preferably 0.5 times the stoichiometric amount with respect to the N-substituted carbamic acid-O-aryl ester. It is removed until double, more preferably 0.1 times aromatic hydroxy compound is present. At this time, it may be removed in the presence of a solvent used in the step (C) described later.
  • Examples of the methyleneated cross-linking agent preferably used in the step (C) include formaldehyde, paraformaldehyde, trioxane, dialkoxymethane having a lower alkyl group having 1 to 6 carbon atoms (for example, dimethoxymethane, diethoxymethane, dioxane). And diacyloxymethane having a lower carboxyl group such as propoxymethane, dipentanoxymethane, dihexyloxymethane), diacetoxymethane, and dipropoxymethane. These may be used alone or in combination of two or more.
  • an aqueous formaldehyde solution is particularly preferable when it is industrially implemented or considering the ease of handling of the methyleneated crosslinking agent.
  • the ratio of the N-substituted carbamic acid-O-mono (aryl ester) to the methyleneated crosslinker is not particularly limited, but the ratio to the methyleneated crosslinker is not limited. It is preferable to use N-substituted carbamic acid-O-monoaryl ester in a stoichiometric ratio of 2 to 20 times. The greater the amount of N-substituted carbamic acid-O-monoaryl ester used, the more the polynuclear body (here, the polynuclear body means that three or more aromatic rings (aromatic rings derived from organic primary amines) are methylene-bridged.
  • N-substituted carbamic acid-O-aryl ester bonded by structure ie, a compound in which m is an integer of 1 or more in the above formula (150)) is suppressed
  • the use amount of the N-substituted carbamic acid-O-monoaryl ester is more preferably in the range of 3 to 15 times, and further preferably in the range of 5 to 10 times, in the stoichiometric ratio with respect to the methyleneated crosslinking agent. .
  • an acid catalyst as a catalyst.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, and organic acids such as formic acid, acetic acid, oxalic acid and toluenesulfonic acid.
  • acids called super strong acids such as hydrobromic acid, perchloric acid, chlorosulfonic acid, and trifluoromethanesulfonic acid are also effective.
  • ion exchange resins having acidic groups such as carboxyl groups and sulfonic acid groups
  • acids called Lewis acids such as trifluoroboric acid, iron chloride, aluminum chloride, zinc chloride, and titanium chloride. .
  • These acids are used in a stoichiometric ratio of 0.001 to 10 with respect to the raw material N-substituted carbamic acid ester in the case of the above-mentioned protonic acids such as inorganic acids, organic acids, and super strong acids.
  • the range is preferably 0.01 to 5.
  • these acids when used as an aqueous solution, they can be used at a concentration in the range of 10 to 95 wt%, preferably in the range of 20 to 80 wt%, with respect to the water in the reaction system. When the concentration is lower than 10 wt%, the reaction rate of the condensation reaction is extremely slow. When the concentration is higher than 95 wt%, undesirable side reactions such as hydrolysis of the raw material may occur.
  • the condensation reaction can be carried out without solvent or in the presence of a solvent.
  • the solvent preferably used include linear, branched, and cyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, hexadecane, cyclopentane, and cyclohexane; benzene, toluene, xylene Aromatic hydrocarbons such as, and their alkyl, halogen, nitro group substituted products; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane; methyl acetate, ethyl acetate Aliphatic ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and the like.
  • thioacetal, acetal or asilal is preferably used because it does not produce free formaldehyde under the reaction conditions and does not substantially produce water by reacting with water produced as a by-product in the reaction.
  • the use of acetals and asylals is preferred.
  • the above-mentioned acid itself is also preferably used as a solvent. These solvents may be used alone or in combination of two or more.
  • These solvents can be used in a range of 0.1 to 100 times, preferably 0.2 to 50 times in weight ratio to the raw material N-substituted carbamic acid-O-monoaryl ester. .
  • the reaction temperature is preferably 10 ° C. to 160 ° C., more preferably 20 to 140 ° C., still more preferably 50 ° C. to 120 ° C.
  • an undesirable side reaction such as hydrolysis may occur.
  • the reaction time varies depending on the reaction method, the compound to be used, and the reaction conditions, it can be carried out in the range of 1 min to 20 hr.
  • reaction solution is sampled, and the reaction is stopped when the amount of reduction of the raw material N-substituted carbamic acid-O-monoaryl ester reaches a certain level by using a known analytical method such as liquid chromatography.
  • a known analytical method such as liquid chromatography.
  • the average molecular weight of the product N-substituted carbamic acid-O-aryl ester reaches a certain level by using a known analysis method such as gel permeation chromatography, for example.
  • the reaction may be stopped.
  • the N-substituted carbamic acid-O-aryl ester obtained by the above method is an N-substituted carbamic acid-O-aryl ester represented by the above formula (150).
  • N-substituted carbamic acid-O-aryl esters considering the ease of handling, particularly the solution viscosity, a compound in which m is 0 among the above-mentioned compounds is preferred. Even if it contains a polynuclear body (that is, a compound in which m is 1 or more in the above formula (150)), there is no problem as long as it does not contradict the purpose of this embodiment.
  • step (F) The N-substituted carbamic acid-O-aryl ester obtained in step (C) is preferably used in step (F).
  • a known method can be used for the removal, and methods such as membrane separation, distillation separation, and crystallization can be used, but distillation separation is preferable.
  • the aromatic hydroxy composition used in the next step (step (F)) is used in the reaction solution of step (C).
  • step (C) is added to form a mixed solution, and the compound remaining in the reaction solution of step (C) (methyleneating agent, reaction solvent, catalyst, etc. used in step (C)) is separated from the mixture by distillation. This is a preferable method because the distillation separation can be carried out without precipitating the N-substituted carbamic acid ester.
  • step (C) since an acid is used, it is necessary to pay attention to the material of the reactor and the condenser. However, as long as the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used. Processes can be added as necessary, and processes and devices in a range that can be assumed by the contractor and the engineer may be added.
  • Route 3) is a route including a method of performing step (R) and performing step (P). First, using a compound having a ureido group, an N-substituted carbamic acid-O—R 2 ester is obtained in step (R), and then, in step (P), the N-substituted carbamic acid-O—R 2 ester and an aromatic compound are obtained. This is a route to react N-substituted carbamic acid-O-aryl ester by reacting with a group hydroxy composition.
  • step (A) a compound having a ureido group (including a reaction solution) is obtained, and using the compound having a ureido group (including a reaction solution), step (R) and then step (P) are performed. This is the route to obtain N-substituted carbamic acid-O-aryl esters.
  • step (R) a compound having a ureido group and an alcohol are reacted to produce an N-substituted carbamic acid—O—R 2 ester. It is a manufacturing process.
  • step of producing an N-substituted carbamic acid-O—R 2 ester by reacting a compound having a ureido group (containing a reaction solution) obtained in step (A) with an alcohol (esterification reaction). is there.
  • FIG. 3 is a conceptual diagram showing the step (R).
  • the compound having a ureido group obtained in step (A) of this route is a compound having a ureido group represented by formula (1) derived from the organic primary amine, and obtained in step (R) of this route.
  • the N-substituted carbamic acid-O—R 2 ester obtained is an N-substituted carbamic acid-O—R 2 ester represented by the formula (49) derived from the compound having the ureido group and the alcohol.
  • the N-substituted carbamic acid-O-aryl ester obtained in the step (P) is an N-substituted carbamic acid-O—R 2 ester represented by the formula (43) derived from the aromatic hydroxy composition. -Substituted carbamic acid-O-aryl ester.
  • the hydroxy composition a used as the reaction solvent in the step (A) is represented by the hydroxy composition in the step (R) (that is, the formula (4) used in the step (R)).
  • the reaction solution obtained in the step (A) is used.
  • the step (R) can be performed as it is.
  • a new hydroxy compound (formula) is added to the reaction solution obtained in step (A).
  • the alcohol represented by (4) and / or the aromatic hydroxy compound represented by formula (2)) may be added to perform step (R), or the reaction liquid obtained in step (A) may be newly added.
  • one or a plurality of hydroxy compounds may be added, and then the step (R) may be performed after part or all of the hydroxy composition used as the reaction solvent in the step (A) is separated. After removing part or all of the hydroxy composition used as the reaction solvent in the step (A), the step (R) may be performed after newly adding one or more hydroxy compounds.
  • the newly added hydroxy compound is an alcohol and / or aromatic hydroxy composition represented by the above formula (4).
  • step (R) When the step (R) is carried out in the presence of an aromatic hydroxy compound, a small amount of N-substituted carbamic acid-O-aryl ester may be produced together with N-substituted carbamic acid-O-R 2 ester.
  • the step (P) described later is performed to perform the N-substituted carbamic acid-O—. Since the R 2 ester is an N-substituted carbamic acid-O-aryl ester, there is no problem.
  • the method of producing an N-substituted carbamic acid-O-alkyl ester by reacting with an alcohol using a compound having a ureido group involves thermally decomposing the N-substituted carbamic acid-O-alkyl ester.
  • Japanese Patent Application Laid-Open No. 6-41045 discloses a method tailored to the purpose of obtaining the corresponding isocyanate and alcohol. As described above, the method includes a range in which a by-product is easily generated in obtaining a compound having a ureido group, and includes a range in which a large amount of N-substituted carbamic acid-O-alkyl ester is generated at the same time.
  • N-substituted carbamic acid-O-alkyl ester is easily heat-denatured and easily produces a compound having a ureylene group. Further, if an isocyanate is produced by pyrolyzing the N-substituted carbamic acid-O-alkyl ester, the pyrolysis temperature becomes high, and the reverse reaction of the pyrolysis reaction is likely to occur, and the pyrolysis reactor is blocked. It is easy to cause.
  • N-substituted carbamic acid-O-aryl ester is obtained by reacting a compound having a ureido group with an aromatic hydroxy compound, N-substituted carbamic acid-O-aryl ester is reduced with little heat denaturation. It has been found that -substituted carbamic acid-O-aryl esters can be obtained.
  • the aromatic hydroxy composition or the aromatic hydroxy compound is selected from the aromatic hydroxy compounds represented by formula (2).
  • the aromatic hydroxy compound represented by the formula (7) is preferable, and the aromatic hydroxy compound represented by the formula (31) is more preferable.
  • a preferred method of using more than one type of aromatic hydroxy compound will be described later, but selection according to the criteria described therein is a preferred method.
  • reaction conditions for producing an N-substituted carbamic acid-O—R 2 ester by reacting a compound having a ureido group with an alcohol in step (R) vary depending on the compound to be reacted, but the amount of alcohol used is The stoichiometric ratio with respect to the ureido group of the compound having a ureido group is in the range of 1 to 500 times. If the amount is less than 1 time, a complicatedly substituted carbonyl compound or a high molecular weight compound having a carbonyl bond in the molecule is likely to be formed. Therefore, it is preferable to use a large excess of alcohol, but the size of the reactor should be considered.
  • the reaction temperature depends on the compound used, but is preferably in the range of 100 ° C to 350 ° C. A temperature lower than 100 ° C. is not preferable because the reaction is slow, the reaction hardly occurs, or the number of complicatedly substituted carbonyl compounds increases. On the other hand, at a temperature higher than 350 ° C., urea (and N-unsubstituted carbamic acid ester) remaining in the step (A) or produced in the system of the step (R) is decomposed or the hydroxy composition is dehydrated.
  • a more preferable temperature is in the range of 120 ° C. to 320 ° C., further preferably in the range of 140 ° C. to 300 ° C.
  • the reaction for producing the N-substituted carbamic acid-O—R 2 ester is an equilibrium reaction, and the reaction is biased toward the original system. Therefore, by-product ammonia is removed from the system as much as possible. It is preferable to carry out the reaction.
  • ammonia is removed so that the ammonia concentration in the reaction solution is 1000 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less, and most preferably 30 ppm or less. Meaning in the liquid phase at the time of implementation).
  • a reactive distillation method a method using an inert gas, a membrane separation, a method using adsorption separation, and the like can be performed.
  • the reactive distillation method is a method in which ammonia that is sequentially generated under the reaction is separated in a gaseous state by distillation. In order to increase the distillation efficiency of ammonia, it can also be carried out under boiling alcohol, solvent or hydroxy composition.
  • the method using an inert gas is a method in which ammonia that is sequentially generated under reaction is separated from a reaction system by being accompanied by an inert gas in a gaseous state.
  • the inert gas for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane or the like is used alone or in combination, and the inert gas is preferably introduced into the reaction system.
  • the adsorbent used in the adsorption separation method include adsorbents that can be used under temperature conditions in which the reaction is performed, such as silica, alumina, various zeolites, and diatomaceous earth. The method for removing these ammonia out of the system may be carried out alone or in combination of a plurality of methods.
  • a catalyst can be used for the purpose of increasing the reaction rate.
  • catalysts include basic catalysts such as lithium, sodium, potassium, calcium, barium methylate, ethylate, butyrate (isomers), rare earth elements, antimony, bismuth, and oxides of these elements. , Sulfides and salts, simple boron and boron compounds, copper group, zinc group, aluminum group, carbon group, titanium group metals and their metal oxides and sulfides in the periodic table, carbon other than carbon in the periodic table Group, titanium, vanadium, and chromium group carbides and nitrides are preferably used.
  • the amount used is not particularly limited, but the catalyst can be used in a stoichiometric ratio of 0.0001 to 100 times the ureido group of the compound having a ureido group. If a catalyst is added, it is often necessary to remove the catalyst. Therefore, it is preferably carried out without adding a catalyst.
  • the reaction pressure varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 Pa to 10 MPa (absolute pressure), which facilitates industrial implementation.
  • the range of 0.1 Pa to 5 MPa (absolute pressure) is more preferable, and in view of removing gaseous ammonia out of the system, 0.1 Pa to 1.5 MPa (absolute pressure) is more preferable.
  • the reaction time (residence time in the case of continuous reaction) varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, the reaction pressure, etc., but is usually from 0.01 to 100 hours.
  • the reaction time can also be determined by the amount of N-substituted carbamic acid-O—R 2 ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) as the target compound.
  • the reaction solution is sampled, and the content of N-substituted carbamic acid ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) in the reaction solution is quantified to have a ureido group
  • the reaction may be stopped after confirming that the compound is produced in a yield of 10% or more, or the reaction may be stopped after confirming that the yield is 90% or more.
  • the reaction solution containing the N-substituted carbamic acid-O—R 2 ester obtained in the step (R) is later converted into an N-substituted carbamic acid-O-aryl ester in a step including the step (P).
  • step (F) an isocyanate is obtained.
  • the yield is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more.
  • reaction solvent for example, pentane (each isomer), hexane (each isomer), heptane (each isomer) ), Octane (each isomer), nonane (each isomer), decane (each isomer), and other alkanes; benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (Each isomer), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; nitrile compounds such as acetonitrile and benzonitrile; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer) Body),
  • aromatic compounds substituted by nitro groups polycyclic hydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, dibenzyltoluene (each isomer); cyclohexane, cyclopentane, cyclooctane, ethyl Aliphatic hydrocarbons such as cyclohexane; Ketones such as methyl ethyl ketone and acetophenone; Esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, and benzyl butyl phthalate; Tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether , Ethers such as diphenyl sulfide and thioethers; ketone compounds such as acetone and methyl ethyl ketone; ester
  • the reaction includes a hydroxy composition and a compound having a carbonyl group derived from urea (N-unsubstituted carbamic acid ester, biuret, etc., a compound inheriting the carbonyl group possessed by urea, And a gas phase containing ammonia by-produced in the reaction and a liquid phase in which the reaction is carried out. Most of the reactions are performed in the liquid phase, but depending on the reaction conditions, the reactions may occur in the gas phase. At that time, the liquid phase volume content in the reactor in which the reaction is carried out is preferably 50% or less.
  • a polymer by-product When the reaction is carried out continuously over a long period of time, a polymer by-product may be generated due to fluctuations in operating conditions (temperature, pressure, etc.), but if the liquid phase volume content in the reactor is large, Such polymeric by-products can be prevented from adhering to and accumulating in the reactor.
  • the liquid phase volume content is too large, the removal efficiency of by-product ammonia is deteriorated and N-substituted carbamic acid-O—R 2 ester (in some cases, N-substituted carbamic acid-O-aryl ester and
  • the liquid phase volume content with respect to the gas phase is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less.
  • the amount is the reaction tank part, in the case of a tower reactor, the stage below the feed stage (not including the tower bottom and reboiler part), and in the thin film distiller, Represents the phase capacity ratio.)
  • the reaction apparatus used for carrying out the reaction is not particularly limited, and a known reactor can be used, but a tank-type and / or tower-type reactor is preferably used. A reactor equipped with a condenser is preferred.
  • the reaction is a system including a gas phase containing a hydroxy composition, a compound having a carbonyl group derived from urea, and ammonia by-produced in the reaction, and a liquid phase for performing the reaction.
  • the liquid phase volume content in the reactor in which the reaction is performed is preferably 50% or less, and the reactor that performs the reaction is also selected to meet the conditions.
  • conventionally known reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination.
  • a well-known condenser can be used.
  • conventionally known condensers such as a multi-tube cylindrical condenser, a double-pipe condenser, a single-pipe condenser, and an air-cooled condenser can be used in appropriate combination.
  • the condenser may be provided inside the reactor, or may be provided outside the reactor and connected to the reactor by piping.
  • the type of the reactor or condenser, the condensate Considering the handling method, etc., various forms are adopted.
  • the material of the reactor and the condenser and known materials can be used.
  • glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used.
  • SUS304, SUS316, SUS316L, etc. are also inexpensive and can be preferably used. If necessary, instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added. A known method such as cooling water or brine can be used. A process may be added as necessary.
  • a step of dissolving a compound having a ureido group in an aromatic hydroxy composition a step of dissolving an aromatic hydroxy compound, a step of separating alcohol, a step of separating and / or purifying an aromatic hydroxy compound, and a generated reaction solution
  • Steps and equipment within the range that can be envisaged by the contractor and the engineer such as a step of purifying the N-substituted carbamic acid-O—R 2 ester from the above, a step of incineration or disposal of by-products and the like, may be added.
  • an N-substituted carbamic acid-O—R 2 ester is produced by reacting a compound having a ureido group and an alcohol in a liquid phase using a reactor (equipped with a condenser). It is a process.
  • the gaseous component containing the compound having a carbonyl group derived from urea and ammonia produced as a by-product in the reaction, which is produced in the step (R) is introduced into a condenser provided in the reactor. Then, a part or all of the alcohol and a compound having a carbonyl group derived from urea are condensed, and ammonia is recovered as a gas.
  • the compound having a carbonyl group derived from urea contained in ammonia recovered as a gas from the condenser is set to a specific amount or less. That is, the ratio of the number of carbonyl groups (—C ( ⁇ O) —) contained in the ammonia-containing compound having a carbonyl group derived from urea to the ammonia molecule is 1 or less, preferably 0.8. 5 or less, more preferably 0.1 or less, and still more preferably 0.01 or less.
  • the reason why the amount of the compound having a carbonyl group derived from urea contained in the ammonia is in a specific range is to avoid adhesion and accumulation of solid components in a line for transferring the ammonia from the condenser. It is.
  • solid components adhering and accumulating in the ammonia transfer line can be identified, as a result of studies by the present inventors, it has been found that most of them are compounds having a carbonyl group.
  • a method of avoiding such adhesion and accumulation of solid components a method of decomposing a compound having a carbonyl group by heating a line for transferring ammonia can be considered, but in the study by the present inventors, only heating is performed.
  • decomposition products for example, isocyanic acid
  • the decomposition products react with compounds having other carbonyl groups, so that the adhesion and accumulation of solid components can be completely avoided. was difficult.
  • the compound having a carbonyl group contained in the ammonia or a decomposition product thereof is rapidly generated particularly at the outlet of the line for transferring ammonia (a portion in contact with the atmosphere). It turned out to be solidified by cooling, and the adhesion and accumulation of solid components were often significant.
  • the present inventors have surprisingly found that the compound having a carbonyl group derived from a carbonic acid derivative contained in the ammonia is not more than the specific amount described above, so that a solid is obtained. It has been found that the problem of component adhesion and accumulation can be solved.
  • the present inventors have a compound having a carbonyl group derived from a carbonic acid derivative or a carbonyl group derived from the carbonic acid derivative for adhesion or accumulation to a line. It is assumed that it is caused by the decomposition and / or polymerization product of the compound, and by making the carbonyl group contained in the compound having a carbonyl group derived from the carbonic acid derivative below a specific concentration, the carbonyl derived from the carbonic acid derivative This is considered to be because the adhesion of the group-containing compound itself and the decomposition and / or polymerization reaction rate of the compound are remarkably reduced.
  • the condensed hydroxy composition and the compound having a carbonyl group derived from urea have a stoichiometric amount with respect to the compound having the carbonyl group derived from the condensed urea.
  • the stoichiometric ratio is 1 or more, preferably the stoichiometric ratio is 2 or more, more preferably the stoichiometric ratio is 3 or more.
  • the reason for this range is that the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea condensed in the condenser can be made into a uniform liquid mixture. This not only facilitates handling of the mixture, but also avoids problems such as adhesion and accumulation of solid components on the condenser.
  • the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea condensed in the condenser in step (R) is circulated inside the reactor to react in the reaction of step (A). May be reused.
  • the amount of ammonia contained in the mixture is preferably 5000 ppm or less, more preferably 3000 ppm or less, and still more preferably 2000 ppm or less.
  • various compounds are recovered as compounds having a carbonyl group derived from urea, but there is no particular limitation on the reuse of these compounds.
  • N-substituted carbamic acid-O—R 2 ester produced by the step (R) can be obtained by subjecting an N-substituted carbamic acid—O—R 2 ester to thermal decomposition.
  • the N-substituted carbamic acid ester used more preferably is N-substituted carbamic acid-O-aryl ester.
  • N-substituted carbamic acid-O-aryl esters are more likely to undergo thermal decomposition reaction than N-substituted carbamic acid-O-R 2 esters, and easily decompose into corresponding isocyanates and aromatic hydroxy compounds. It is known to do.
  • step (P) an N-substituted carbamic acid-O-aryl ester that is easily thermally decomposed is converted by an ester exchange reaction and then used for an isocyanate reaction. Since this step is a step of converting the ester group of the N-substituted carbamic acid-O—R 2 ester, it is also referred to as “transesterification step” in the present embodiment.
  • an aromatic hydroxy composition a composition containing at least one aromatic hydroxy compound represented by the following formula (2)
  • a reaction transesterification reaction
  • FIG. 4 is a conceptual diagram showing the step (P).
  • an alcohol derived from N-substituted carbamic acid-O—R 2 ester is generated.
  • the target N-substituted carbamic acid-R 2 ester is an N-substituted carbamic acid-O—R 2 ester represented by the above formula (49).
  • the aromatic hydroxy compound in the aromatic hydroxy composition to be reacted is represented by the above formula (2), formula (7), formula (31), formula (32), formula (38), formula (39), formula (40). Any of the aromatic hydroxy compounds represented by the above may be used.
  • the aromatic hydroxy compound represented by the formula (7) or the formula (31) is included, and more preferably an aromatic hydroxy composition including the active aromatic hydroxy compound represented by the formula (32) is used. More preferably, an aromatic hydroxy composition containing an active aromatic hydroxy compound represented by formula (38) is used.
  • step (P) various methods can be performed according to the compounds to be used with reference to known methods (for example, refer to WO2008 / 059953).
  • the reaction conditions in the step (P) vary depending on the compound to be reacted, but the aromatic hydroxy compound in the aromatic hydroxy composition is added to the ester group constituting the raw material N-substituted carbamic acid-O—R 2 ester. Expressed in stoichiometric ratio, it is used in the range of 2 to 1000 times.
  • the aromatic hydroxy compound is preferably in an excess amount with respect to the ester group constituting the N-substituted carbamic acid-O—R 2 ester of the raw material. In consideration, it is preferably in the range of 2 to 100 times, more preferably in the range of 5 to 50 times.
  • the reaction temperature is usually in the range of 100 ° C. to 300 ° C., and a high temperature is preferable for increasing the reaction rate. On the other hand, a side reaction tends to occur at a high temperature, and preferably 150 ° C. to 250 ° C. It is in the range of ° C.
  • a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually in the range of 20 to 1 ⁇ 10 6 Pa.
  • the reaction time (retention time in the case of a continuous process) is not particularly limited, and is usually 0.001 to 100 hours, preferably 0.01 to 50 hours, more preferably 0.1 to 30 hours.
  • the reaction solution can be collected and the reaction can be terminated after confirming that the desired amount of the desired N-substituted carbamic acid-O-aryl ester has been formed by, for example, liquid chromatography.
  • a catalyst is not always necessary, but there is no problem in using the catalyst in order to lower the reaction temperature or complete the reaction at an early stage.
  • the catalyst is used in an amount of 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the weight of the N-substituted carbamic acid-O—R 2 ester.
  • the catalyst examples include Lewis acids and Lewis Transition metal compounds that generate acids, organotin compounds, copper group metals, zinc, iron group metal compounds, specifically, AlX 3 , TiX 3 , TiX 4 , VOX 3 , VX 5 , ZnX 2 , FeX 3 , A Lewis acid represented by SnX 4 (where X is a halogen, an acetoxy group, an alkoxy group, an aryloxy group) and a transition metal compound that generates a Lewis acid; (CH 3 ) 3 SnOCOCH 3 , (C 2 H 5 ) SnOCOC 6 H 5, Bu 3 SnOCOCH 3, Ph 3 SnOCOCH 3, Bu 2 Sn (OCOCH 3) 2, Bu 2 Sn (OCOC 11 H 23 2, Ph 3 SnOCH 3, ( C 2 H 5) 3 SnOPh, Bu 2 Sn (OCH 3) 2, Bu 2 Sn (OC 2 H 5) 2, Bu 2 Sn (OPh) 2, Ph 2 Sn (CH 3 ) 2 , (
  • these compounds may be used alone or as a mixture of two or more.
  • an appropriate inert solvent such as hexane (each isomer), heptane (each isomer), for example, for the purpose of facilitating the reaction operation, Alkanes such as octane (each isomer), nonane (each isomer), decane (each isomer); benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each Isomers), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; chlorobenzene, dichloro
  • the transesterification reaction in the present embodiment is an equilibrium reaction. Therefore, in order to perform transesterification efficiently, it is preferable to proceed the reaction while removing the product alcohol (alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester) from the reaction system. Therefore, the aromatic hydroxy compound is selected so that the standard boiling point of the aromatic hydroxy compound used in the transesterification is higher than the standard boiling point of the alcohol derived from the N-substituted carbamic acid-O—R 2 ester of the raw material.
  • the compound having the lowest standard boiling point in the reaction system becomes an alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester, and the product can be easily removed from the reaction system.
  • the two components to be separated have a normal boiling point of 10 ° C. or more and can be distilled and separated industrially, the most in the aromatic hydroxy composition is higher than the normal boiling point of the alcohol. It is preferable to use an aromatic hydroxy compound having a low boiling point (compared with the normal boiling point) and having a standard boiling point of 10 ° C. or higher.
  • transesterification is preferably performed by a continuous method. That is, a raw material N-substituted carbamic acid-O—R 2 ester and an aromatic hydroxy composition are continuously supplied to a reactor to perform transesterification to produce a raw material N-substituted carbamic acid-O.
  • the alcohol derived from —R 2 ester is removed from the reactor as a gas component, and the resulting reaction solution containing the N-substituted carbamic acid-O-aryl ester and the aromatic hydroxy composition is continuously removed from the bottom of the reactor. .
  • the material of the reactor and line for performing the transesterification may be any known material as long as it does not adversely affect the starting materials and the reactants.
  • SUS304, SUS316, SUS316L, etc. are inexpensive and preferably used. it can.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary.
  • a step of dissolving an aromatic hydroxy compound For example, a step of dissolving an aromatic hydroxy compound, a step of separating an alcohol, a step of separating and / or purifying an aromatic hydroxy compound, a step of purifying an N-substituted carbamic acid-O-aryl ester from the produced reaction solution, You may add the process and apparatus of the range which the said contractor and the said engineer can assume, such as the process of incinerating or discarding a by-product.
  • limiting in particular in the form of a reactor A well-known tank-like and tower-like reactor can be used.
  • stirring tank for example, stirring tank, multistage stirring tank, distillation tower, multistage distillation tower, multitubular reactor, continuous multistage distillation tower, packed tower, thin film evaporator, reactor with support inside, forced circulation reactor, falling film
  • a method using a reactor including any of an evaporator, a drop evaporator, a trickle phase reactor, and a bubble column, and a combination of these may be used.
  • a method using a thin film evaporator or a columnar reactor is preferred, and it is derived from the raw material N-substituted carbamic acid-O—R 2 ester to be produced.
  • the multi-stage distillation column is a distillation column having a multi-stage of two or more theoretical distillation stages, and any column can be used as long as continuous distillation is possible.
  • Examples of such a multi-stage distillation column include a tray column type using a bubble tray, a perforated plate tray, a valve tray, a counter-flow tray, etc., a Raschig ring, a lessing ring, a pole ring, a Berle saddle, an interlocks.
  • Any of those usually used as a multistage distillation column can be used, such as a packed column type packed with various packings such as saddle, Dixon packing, McMahon packing, helipak, sulzer packing, and melapack.
  • Any packed tower can be used as long as it is a packed tower in which the above-mentioned known filler is packed in the tower.
  • a shelf-packed mixing type having both a shelf portion and a portion filled with a packing is also preferably used.
  • a line for supplying an inert gas and / or a liquid inert solvent from the bottom of the reactor may be separately attached, or a mixture containing the target N-substituted carbamic acid-O-aryl ester and an aromatic hydroxy compound
  • the liquid contains a raw material N-substituted carbamic acid-O—R 2 ester
  • a line for circulating part or all of the mixed liquid to the reactor may be attached.
  • this inert solvent may be gaseous and / or liquid.
  • the gaseous component containing the alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester extracted from the reactor is preferably purified using a known method such as a distillation column to obtain the steps (A) and / or Or it can recycle
  • Route 4) is a method of performing step (R), performing step (P), and performing step (C). Route 4) is also an aspect of the method shown in route 2).
  • the organic primary amine used in the step (A) is an aromatic organic monoprimary amine represented by the following formula (5), and after the step (P), the following step (C From the N-substituted carbamic acid-O-aryl ester obtained in step (P), at least two molecules of the N-substituted carbamic acid-O-aryl ester are methylene groups (—CH 2 —). This is a method for obtaining a crosslinked, N-substituted carbamic acid-O-aryl ester.
  • the aromatic hydroxy compound constituting the aromatic hydroxy composition used in step (A) and / or step (R) and / or step (P) uses an aromatic monohydroxy compound.
  • At least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are obtained by crosslinking an aromatic group derived from an aromatic organic monoprimary amine contained in the ester with a methylene group (—CH 2 —).
  • the N- substituted carbamic acid -O-R 2 esters in this route 4) shows the N- substituted carbamic acid -O-R 2 ester unreacted in step (P).
  • the organic primary amine is subjected to the step (A) using the organic primary amine represented by the following formula, and the ureido group represented by the formula (1) derived from the organic primary amine is represented. And then performing step (R) to obtain an N-substituted carbamic acid-O—R 2 ester derived from the compound having the ureido group, and then performing step (P) to remove the ureido group.
  • step (C) N-substituted carbamic acid-O-aryl ester derived from the compound having is obtained, and then step (C) is carried out. That is, the organic primary amine used in this route is the organic primary amine represented by the formula (5), and the compound having a ureido group obtained in the step (A) of this route is the organic primary amine.
  • —O—R 2 ester more specifically, N-substituted carbamic acid —O—R 2 ester represented by the following formula (146), which is obtained in the step (P) of this route.
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with an aromatic ring.
  • R 3 to R 6 groups may be formed of a hydrogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aryl group having a hydroxy group, a saturated aliphatic bond and / or an ether
  • the total number of carbon atoms constituting the mono primary amine is 6 to 13 It consists of an integer number.
  • the compound having a ureido group obtained in the step (A) is a compound having at least one ureido group represented by the following formula (148).
  • R 3, R 4, R 5 , R 6 groups of formula (148) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5)
  • a compound in which the amino group (—NH 2 group) of the organic primary amine represented by the formula (5) is a ureido group (—NH—CO—NH 2 ).
  • At least one position of the ortho-position and / or para-position of the ureido group of the N-substituted aromatic organic monourea represented by the formula (148) is unsubstituted, and the R 3 to R 6 groups each have aromaticity of the ring R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with the aromatic ring.
  • the R 3 to R 6 groups may be formed of a hydrogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aryl group having a hydroxy group, a saturated aliphatic bond and / or an ether
  • R 3 to R 6 are groups selected from a group composed of a group bonded by a bond, and are groups having an integer range of 0 to 7 carbon atoms, and N— represented by the formula (148) Ureides constituting substituted aromatic organic monoureas The total number of carbon atoms excluding the group (—NH—CO—NH 2 ) is composed of 6 to 13. )
  • R 2 to R 6 groups are the groups shown above.
  • step (R) is performed, and the N-substituted carbamic acid-O-aryl ester obtained in step (P) is at least one N-substituted carbamic acid-O represented by the following formula (149).
  • R 3, R 4, R 5 , R 6 groups of formula (149) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5)
  • a ureido group (—NH—CO—NH 2 ) of a compound having a ureido group represented by formula (148) is a carbamic acid-O-aryl ester group.
  • R 3 to R 6 groups are the groups indicated above.
  • Steps (A) and (R) and Step (P) of this route the organic primary amine used is Formula (5), and Step (A), Step (R) and Step (P) of this route are The process is performed under the conditions of the process (A), the process (R) and the process (P) of the route 3.
  • reaction conditions for producing an N-substituted carbamic acid-O—R 2 ester by reacting a compound having a ureido group with an alcohol in step (R) vary depending on the compound to be reacted, but the amount of alcohol used is The stoichiometric ratio with respect to the ureido group of the compound having a ureido group is in the range of 1 to 500 times. If the amount is less than 1 time, a complicatedly substituted carbonyl compound or a high molecular weight compound having a carbonyl bond in the molecule is likely to be formed. Therefore, it is preferable to use a large excess of alcohol.
  • reaction temperature depends on the compound used, but is preferably in the range of 100 ° C to 350 ° C. A temperature lower than 100 ° C. is not preferable because the reaction is slow, the reaction hardly occurs, or the number of complicatedly substituted carbonyl compounds increases. On the other hand, at a temperature higher than 350 ° C., urea (and N-unsubstituted carbamic acid ester) remaining in the step (A) or produced in the system of the step (R) is decomposed or the hydroxy composition is dehydrated.
  • a more preferable temperature is in the range of 120 ° C. to 320 ° C., further preferably in the range of 140 ° C. to 300 ° C.
  • the reaction for producing the N-substituted carbamic acid-O—R 2 ester is an equilibrium reaction, and the reaction is biased toward the original system. Therefore, by-product ammonia is removed from the system as much as possible. It is preferable to carry out the reaction. Preferably, ammonia is removed so that the ammonia concentration in the reaction solution is 1000 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less, and most preferably 30 ppm or less. Meaning in the liquid phase at the time of implementation).
  • a reactive distillation method, a method using an inert gas, a membrane separation, a method using adsorption separation, and the like can be performed.
  • the reactive distillation method is a method in which ammonia that is sequentially generated under the reaction is separated in a gaseous state by distillation. In order to increase the distillation efficiency of ammonia, it can also be carried out under boiling alcohol, solvent or hydroxy composition.
  • the method using an inert gas is a method in which ammonia that is sequentially generated under reaction is separated from a reaction system by being accompanied by an inert gas in a gaseous state.
  • the inert gas for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane or the like is used alone or in combination, and the inert gas is preferably introduced into the reaction system.
  • Examples of the adsorbent used in the adsorption separation method include adsorbents that can be used under temperature conditions in which the reaction is performed, such as silica, alumina, various zeolites, and diatomaceous earth.
  • the method for removing these ammonia out of the system may be carried out alone or in combination of a plurality of methods.
  • a catalyst can be used for the purpose of increasing the reaction rate.
  • catalysts include basic catalysts such as lithium, sodium, potassium, calcium, barium methylate, ethylate, butyrate (isomers), rare earth elements, antimony, bismuth, and oxides of these elements. , Sulfides and salts, simple boron and boron compounds, copper group, zinc group, aluminum group, carbon group, titanium group metals and their metal oxides and sulfides in the periodic table, carbon other than carbon in the periodic table Group, titanium, vanadium, and chromium group carbides and nitrides are preferably used.
  • the amount used is not particularly limited, but the catalyst can be used in a stoichiometric ratio of 0.0001 to 100 times the ureido group of the compound having a ureido group.
  • the reaction pressure varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 Pa to 10 MPa (absolute pressure), which facilitates industrial implementation. In view of the properties, the range of 0.1 Pa to 5 MPa (absolute pressure) is more preferable, and in view of removing gaseous ammonia out of the system, 0.1 Pa to 1.5 MPa (absolute pressure) is more preferable.
  • the reaction time (residence time in the case of continuous reaction) varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, the reaction pressure, etc., but is usually from 0.01 to 100 hours.
  • the reaction time can also be determined by the amount of N-substituted carbamic acid-O—R 2 ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) as the target compound.
  • the reaction solution is sampled, and the content of N-substituted carbamic acid ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) in the reaction solution is quantified to have a ureido group
  • the reaction may be stopped after confirming that the compound is produced in a yield of 10% or more, or the reaction may be stopped after confirming that the yield is 90% or more.
  • the reaction solution containing the N-substituted carbamic acid-O—R 2 ester obtained in the step (R) is later converted into an N-substituted carbamic acid-O-aryl ester in a step including the step (P).
  • step (F) an isocyanate is obtained.
  • the yield is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more.
  • reaction solvent for example, pentane (each isomer), hexane (each isomer), heptane (each isomer) ), Octane (each isomer), nonane (each isomer), decane (each isomer), and other alkanes; benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (Each isomer), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; nitrile compounds such as acetonitrile and benzonitrile; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer) Body),
  • aromatic compounds substituted by nitro groups polycyclic hydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, dibenzyltoluene (each isomer); cyclohexane, cyclopentane, cyclooctane, ethyl Aliphatic hydrocarbons such as cyclohexane; Ketones such as methyl ethyl ketone and acetophenone; Esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, and benzyl butyl phthalate; Tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether , Ethers such as diphenyl sulfide and thioethers; ketone compounds such as acetone and methyl ethyl ketone; ester
  • the reaction includes a hydroxy composition, a compound having a carbonyl group derived from urea (N-unsubstituted carbamic acid ester, biuret, etc., a compound that inherits the carbonyl group possessed by urea, and N-substituted carbamic acid And a gas phase containing ammonia produced as a by-product in the reaction, and a liquid phase in which the reaction is carried out. Most of the reactions are performed in the liquid phase, but depending on the reaction conditions, the reactions may occur in the gas phase. At that time, the liquid phase volume content in the reactor in which the reaction is carried out is preferably 50% or less.
  • a polymer by-product When the reaction is carried out continuously over a long period of time, a polymer by-product may be generated due to fluctuations in operating conditions (temperature, pressure, etc.), but if the liquid phase volume content in the reactor is large, Such polymeric by-products can be prevented from adhering to and accumulating in the reactor.
  • the liquid phase volume content is too large, the removal efficiency of by-product ammonia is deteriorated and N-substituted carbamic acid-O—R 2 ester (in some cases, N-substituted carbamic acid-O-aryl ester and
  • the liquid phase volume content with respect to the gas phase is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less.
  • the amount is the reaction tank part, in the case of a tower reactor, the stage below the feed stage (not including the tower bottom and reboiler part), and in the thin film distiller, Represents the phase capacity ratio.)
  • the reaction apparatus used for carrying out the reaction is not particularly limited, and a known reactor can be used, but a tank-type and / or tower-type reactor is preferably used.
  • a reactor equipped with a condenser is preferred.
  • the reaction is a system including a gas phase containing a hydroxy composition, a compound having a carbonyl group derived from urea, and ammonia by-produced in the reaction, and a liquid phase for performing the reaction.
  • the liquid phase volume content in the reactor in which the reaction is performed is preferably 50% or less, and the reactor that performs the reaction is also selected to meet the conditions.
  • reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination.
  • a well-known condenser can be used.
  • conventionally known condensers such as a multi-tube cylindrical condenser, a double-pipe condenser, a single-pipe condenser, and an air-cooled condenser can be used in appropriate combination.
  • the condenser may be provided inside the reactor, or may be provided outside the reactor and connected to the reactor by piping.
  • the type of the reactor or condenser, the condensate Considering the handling method, etc. various forms are adopted.
  • the material of the reactor and the condenser and known materials can be used.
  • glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used.
  • SUS304, SUS316, SUS316L, etc. are also inexpensive and can be preferably used.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary.
  • a step of dissolving a compound having a ureido group in an aromatic hydroxy composition a step of dissolving an aromatic hydroxy compound, a step of separating alcohol, a step of separating and / or purifying an aromatic hydroxy compound, and a generated reaction solution
  • Steps and equipment within the range that can be envisaged by the contractor and the engineer such as a step of purifying the N-substituted carbamic acid-O—R 2 ester from the above, a step of incineration or disposal of by-products and the like, may be added.
  • a compound having a ureido group and an alcohol are reacted in a liquid phase (esterification reaction) using a reactor (provided with a condenser) to produce an N-substituted carbamic acid-O—R.
  • This is a process for producing 2- ester.
  • the gaseous component containing the compound having a carbonyl group derived from urea and ammonia produced as a by-product in the reaction, which is produced in the step (R) is introduced into a condenser provided in the reactor. Then, a part or all of the alcohol and a compound having a carbonyl group derived from urea are condensed, and ammonia is recovered as a gas.
  • the compound having a carbonyl group derived from urea contained in ammonia recovered as a gas from the condenser is set to a specific amount or less. That is, the ratio of the number of carbonyl groups (—C ( ⁇ O) —) contained in the ammonia-containing compound having a carbonyl group derived from urea to the ammonia molecule is 1 or less, preferably 0.8. 5 or less, more preferably 0.1 or less, and still more preferably 0.01 or less.
  • the reason why the amount of the compound having a carbonyl group derived from urea contained in the ammonia is in a specific range is to avoid adhesion and accumulation of solid components in a line for transferring the ammonia from the condenser. It is.
  • solid components adhering and accumulating in the ammonia transfer line can be identified, as a result of studies by the present inventors, it has been found that most of them are compounds having a carbonyl group.
  • a method of avoiding such adhesion and accumulation of solid components a method of decomposing a compound having a carbonyl group by heating a line for transferring ammonia can be considered, but in the study by the present inventors, only heating is performed.
  • decomposition products for example, isocyanic acid
  • the decomposition products react with compounds having other carbonyl groups, so that the adhesion and accumulation of solid components can be completely avoided. was difficult.
  • the compound having a carbonyl group contained in the ammonia or a decomposition product thereof is rapidly generated particularly at the outlet of the line for transferring ammonia (a portion in contact with the atmosphere). It turned out to be solidified by cooling, and the adhesion and accumulation of solid components were often significant.
  • the present inventors have surprisingly found that the compound having a carbonyl group derived from a carbonic acid derivative contained in the ammonia is not more than the specific amount described above, so that a solid is obtained. It has been found that the problem of component adhesion and accumulation can be solved.
  • the present inventors have a compound having a carbonyl group derived from a carbonic acid derivative or a carbonyl group derived from the carbonic acid derivative for adhesion or accumulation to a line. It is assumed that it is caused by the decomposition and / or polymerization product of the compound, and by making the carbonyl group contained in the compound having a carbonyl group derived from the carbonic acid derivative below a specific concentration, the carbonyl derived from the carbonic acid derivative This is considered to be because the adhesion of the group-containing compound itself and the decomposition and / or polymerization reaction rate of the compound are remarkably reduced.
  • the condensed hydroxy composition and the compound having a carbonyl group derived from urea have a stoichiometric amount relative to the compound having the carbonyl group derived from the condensed urea.
  • the stoichiometric ratio is 1 or more, preferably the stoichiometric ratio is 2 or more, more preferably the stoichiometric ratio is 3 or more.
  • the reason for this range is that the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea that is condensed in the condenser can be a uniform liquid mixture. This not only facilitates handling of the mixture, but also avoids problems such as adhesion and accumulation of solid components on the condenser.
  • the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea condensed in the condenser in step (R) is circulated inside the reactor to react in the reaction of step (A). May be reused.
  • the amount of ammonia contained in the mixture is preferably 5000 ppm or less, more preferably 3000 ppm or less, and still more preferably 2000 ppm or less.
  • FIG. 5 is a conceptual diagram showing the step (P).
  • the step (P) an alcohol derived from N-substituted carbamic acid-O—R 2 ester is generated.
  • the step (P) will be described.
  • the aromatic hydroxy compound in the aromatic hydroxy composition to be reacted is represented by the above formula (2), formula (7), formula (31), formula (32), formula (38), formula (39), formula (40). Any of the aromatic hydroxy compounds represented by the above may be used.
  • the aromatic hydroxy compound represented by the formula (7) or the formula (31) is contained, and more preferably, an aromatic hydroxy composition containing the active aromatic hydroxy compound represented by the formula (32) is used. More preferably, an aromatic hydroxy composition containing an active aromatic hydroxy compound represented by formula (38) is used.
  • step (P) various methods can be performed according to the compounds to be used with reference to known methods (for example, refer to WO2008 / 059953).
  • the reaction conditions in the step (P) vary depending on the compound to be reacted, but the aromatic hydroxy compound in the aromatic hydroxy composition is added to the ester group constituting the raw material N-substituted carbamic acid-O—R 2 ester. Expressed in stoichiometric ratio, it is used in the range of 2 to 1000 times.
  • the aromatic hydroxy compound is preferably in an excess amount relative to the ester group constituting the N-substituted carbamic acid-O—R 2 ester of the raw material. In consideration, it is preferably in the range of 2 to 100 times, more preferably in the range of 5 to 50 times.
  • the reaction temperature is usually in the range of 100 ° C. to 300 ° C., and a high temperature is preferable for increasing the reaction rate. On the other hand, a side reaction tends to occur at a high temperature, and preferably 150 ° C. to 250 ° C. It is in the range of ° C.
  • a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually in the range of 20 to 1 ⁇ 10 6 Pa.
  • the reaction time (retention time in the case of a continuous process) is not particularly limited, and is usually 0.001 to 100 hours, preferably 0.01 to 50 hours, more preferably 0.1 to 30 hours.
  • the reaction solution can be collected and the reaction can be terminated after confirming that the desired amount of the desired N-substituted carbamic acid-O-aryl ester has been formed by, for example, liquid chromatography.
  • a catalyst is not always necessary, but there is no problem in using the catalyst in order to lower the reaction temperature or complete the reaction at an early stage.
  • the catalyst is used in an amount of 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the weight of the N-substituted carbamic acid-O—R 2 ester.
  • the catalyst examples include Lewis acids and Lewis Transition metal compounds that generate acids, organotin compounds, copper group metals, zinc, iron group metal compounds, specifically, AlX 3 , TiX 3 , TiX 4 , VOX 3 , VX 5 , ZnX 2 , FeX 3 , A Lewis acid represented by SnX 4 (where X is a halogen, an acetoxy group, an alkoxy group, an aryloxy group) and a transition metal compound that generates a Lewis acid; (CH 3 ) 3 SnOCOCH 3 , (C 2 H 5 ) SnOCOC 6 H 5, Bu 3 SnOCOCH 3, Ph 3 SnOCOCH 3, Bu 2 Sn (OCOCH 3) 2, Bu 2 Sn (OCOC 11 H 23 2, Ph 3 SnOCH 3, ( C 2 H 5) 3 SnOPh, Bu 2 Sn (OCH 3) 2, Bu 2 Sn (OC 2 H 5) 2, Bu 2 Sn (OPh) 2, Ph 2 Sn (CH 3 ) 2 , (
  • an appropriate inert solvent such as hexane (each isomer), heptane (each isomer), for example, for the purpose of facilitating the reaction operation, Alkanes such as octane (each isomer), nonane (each isomer), decane (each isomer); benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each Isomers), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer), chloronaphthalene, bromonaphthalene, nitrobenzene, nitro Aromatic compounds
  • the transesterification reaction in the present embodiment is an equilibrium reaction. Therefore, in order to perform transesterification efficiently, it is preferable to proceed the reaction while removing the product alcohol (alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester) from the reaction system. Therefore, the aromatic hydroxy compound is selected so that the standard boiling point of the aromatic hydroxy compound used in the transesterification is higher than the standard boiling point of the alcohol derived from the N-substituted carbamic acid-O—R 2 ester of the raw material.
  • the compound having the lowest standard boiling point in the reaction system becomes an alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester, and the product can be easily removed from the reaction system.
  • the two components to be separated have a normal boiling point of 10 ° C. or more and can be distilled and separated industrially, the most in the aromatic hydroxy composition is higher than the normal boiling point of the alcohol. It is preferable to use an aromatic hydroxy compound having a low boiling point (compared with the normal boiling point) and having a standard boiling point of 10 ° C. or higher.
  • transesterification is preferably performed by a continuous method. That is, a raw material N-substituted carbamic acid-O—R 2 ester and an aromatic hydroxy composition are continuously supplied to a reactor to perform transesterification to produce a raw material N-substituted carbamic acid-O.
  • the alcohol derived from —R 2 ester is removed from the reactor as a gas component, and the resulting reaction solution containing the N-substituted carbamic acid-O-aryl ester and the aromatic hydroxy composition is continuously removed from the bottom of the reactor. .
  • the material of the reactor and line for performing the transesterification may be any known material as long as it does not adversely affect the starting materials and the reactants.
  • SUS304, SUS316, SUS316L, etc. are inexpensive and preferably used. it can.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary.
  • a step of dissolving an aromatic hydroxy compound For example, a step of dissolving an aromatic hydroxy compound, a step of separating an alcohol, a step of separating and / or purifying an aromatic hydroxy compound, a step of purifying an N-substituted carbamic acid-O-aryl ester from the produced reaction solution, You may add the process and apparatus of the range which the said contractor and the said engineer can assume, such as the process of incinerating or discarding a by-product.
  • limiting in particular in the form of a reactor A well-known tank-like and tower-like reactor can be used.
  • stirring tank for example, stirring tank, multistage stirring tank, distillation tower, multistage distillation tower, multitubular reactor, continuous multistage distillation tower, packed tower, thin film evaporator, reactor with support inside, forced circulation reactor, falling film
  • a method using a reactor including any of an evaporator, a drop evaporator, a trickle phase reactor, and a bubble column, and a combination of these may be used.
  • a method using a thin film evaporator or a columnar reactor is preferred, and it is derived from the raw material N-substituted carbamic acid-O—R 2 ester to be produced.
  • the multi-stage distillation column is a distillation column having a multi-stage of two or more theoretical distillation stages, and any column can be used as long as continuous distillation is possible.
  • Examples of such a multi-stage distillation column include a tray column type using a bubble tray, a perforated plate tray, a valve tray, a counter-flow tray, etc., a Raschig ring, a lessing ring, a pole ring, a Berle saddle, an interlocks.
  • Any of those usually used as a multistage distillation column can be used, such as a packed column type packed with various packings such as saddle, Dixon packing, McMahon packing, helipak, sulzer packing, and melapack.
  • Any packed tower can be used as long as it is a packed tower in which the above-mentioned known filler is packed in the tower.
  • a shelf-packed mixing type having both a shelf portion and a portion filled with a packing is also preferably used.
  • a line for supplying an inert gas and / or a liquid inert solvent from the bottom of the reactor may be separately attached, or a mixture containing the target N-substituted carbamic acid-O-aryl ester and an aromatic hydroxy compound
  • the liquid contains a raw material N-substituted carbamic acid-O—R 2 ester
  • a line for circulating part or all of the mixed liquid to the reactor may be attached again.
  • this inert solvent may be gaseous and / or liquid.
  • the gaseous component containing the alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester extracted from the reactor is preferably purified using a known method such as a distillation column to obtain the steps (A) and / or Or it can recycle
  • step (C) at least one N-substituted carbamic acid-O-aryl ester (containing a reaction solution) obtained in the step (P) is crosslinked with a methylene group (—CH 2 —), and at least two molecules
  • the N-substituted carbamic acid —O— (R 2 or aryl) ester is crosslinked with a methylene group (—CH 2 —) to obtain an N-substituted carbamic acid —O— (R 2 or aryl) ester.
  • step (C) at least one molecule of the N-substituted carbamic acid-O-aryl ester represented by the following formula (150) was crosslinked with the methylene group (—CH 2 —). N-substituted carbamic acid-O-aryl ester is obtained.
  • a polyvalent aromatic hydroxy compound may be used. Cross-linking may occur at this location.
  • aromatic monohydroxy compound represented by the formula (31) is preferable, more preferably an active aromatic hydroxy compound represented by the formula (38) is used, and still more preferably, Among the active aromatic hydroxy compounds represented by the formula (38), an aromatic monohydroxy compound in which the R 26 and R 27 groups are hydrogen atoms and the other substituents are chain and / or cyclic saturated alkyl groups.
  • Ring A is a group derived from an aromatic hydroxy compound constituting the aromatic hydroxy composition as defined above, and is a group of hydroxyl groups directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound. Represents a residue with one hydrogen atom removed,
  • the R 3 to R 6 groups represent the groups defined above; m is an integer of 0 to 6.
  • the N-substituted carbamic acid-O-mono (aryl ester) represented by the above formula (149) can be directly subjected to a thermal decomposition reaction to produce a monoisocyanate.
  • the isocyanate is preferably a polyfunctional isocyanate. Therefore, there is a method of obtaining a polyfunctional isocyanate by subjecting the N-substituted carbamic acid mono (aryl ester) to a multimer in advance by the above step (C) and then subjecting the multimer to a thermal decomposition reaction. Can be done.
  • N-substituted carbamic acid-O-aryl ester obtained in the step (P) of route 4) is often referred to as N-substituted carbamic acid-O-mono (aryl ester) or N-substituted carbamic acid monoaryl ester.
  • the step (C) can be carried out by a known method (for example, refer to German Patent No. 1042891).
  • the aromatic hydroxy composition used in step (P) is separated from the resulting reaction solution containing the N-substituted carbamic acid-O-aryl ester.
  • the step (C) may be performed in the presence of an aromatic hydroxy compound, the aromatic hydroxy compound may also be cross-linked with a methyleneated cross-linking agent to produce a by-product such as a polyaromatic hydroxy compound.
  • the amount of the methyleneated cross-linking agent used may be increased, so that the aromatic hydroxy compound is preferably separated.
  • the separation method may be a known method, and varies depending on the compound to be used.
  • the separation method is a method using distillation or extraction and separation using the difference in solubility between the N-substituted carbamic acid-O-aryl ester and the aromatic hydroxy compound.
  • the amount of the aromatic hydroxy compound after the above separation operation is 1 time or less in terms of stoichiometric amount with respect to the N-substituted carbamic acid-O-aryl ester, preferably 0.8. Remove until 5 times, more preferably 0.1 times aromatic hydroxy compound is present. At this time, it may be removed in the presence of a solvent used in the step (C) described later.
  • Examples of the methyleneated crosslinking agent preferably used in the step (C) include formaldehyde, paraformaldehyde, trioxane, dialkoxymethane having a lower alkyl group having 1 to 6 carbon atoms (for example, dimethoxymethane, diethoxymethane, dioxane). And diacyloxymethane having a lower carboxyl group such as propoxymethane, dipentanoxymethane, dihexyloxymethane), diacetoxymethane, and dipropoxymethane. These may be used alone or in combination of two or more.
  • the ratio of the N-substituted carbamic acid-O-mono (aryl ester) to the methyleneated crosslinker is not particularly limited, but the ratio to the methyleneated crosslinker is not limited. It is preferable to use N-substituted carbamic acid-O-monoaryl ester in a stoichiometric ratio of 2 to 20 times.
  • N-substituted carbamic acid-O-monoaryl ester used, the more the polynuclear body (here, the polynuclear body means that three or more aromatic rings (aromatic rings derived from organic primary amines) are methylene-bridged.
  • N-substituted carbamic acid-O-aryl ester bonded by structure that is, a compound in which m is an integer of 1 or more in the above formula (150) is suppressed,
  • the residual amount of the starting N-substituted carbamic acid-O-mono (aryl ester) often increases.
  • the amount of N-substituted carbamic acid-O-monoaryl ester used is preferably in the range of 3 to 15 times, more preferably in the range of 5 to 10 times, as a stoichiometric ratio with respect to the methyleneated crosslinking agent.
  • an acid catalyst as a catalyst.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, and organic acids such as formic acid, acetic acid, oxalic acid and toluenesulfonic acid.
  • acids called super strong acids such as hydrobromic acid, perchloric acid, chlorosulfonic acid, and trifluoromethanesulfonic acid are also effective.
  • ion exchange resins having acidic groups such as carboxyl groups and sulfonic acid groups
  • acids called Lewis acids such as trifluoroboric acid, iron chloride, aluminum chloride, zinc chloride, and titanium chloride. .
  • These acids are used in a stoichiometric ratio of 0.001 to 10 with respect to the raw material N-substituted carbamic acid ester in the case of the above-mentioned protonic acids such as inorganic acids, organic acids, and super strong acids.
  • the range is preferably 0.01 to 5.
  • these acids when used as an aqueous solution, they can be used at a concentration in the range of 10 to 95 wt%, preferably in the range of 20 to 80 wt%, with respect to the water in the reaction system. When the concentration is lower than 10 wt%, the reaction rate of the condensation reaction is extremely slow. When the concentration is higher than 95 wt%, undesirable side reactions such as hydrolysis of the raw material may occur.
  • the condensation reaction can be carried out without solvent or in the presence of a solvent.
  • the solvent preferably used include linear, branched, and cyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, hexadecane, cyclopentane, and cyclohexane; benzene, toluene, xylene And their aromatic, halogen, and nitro group-substituted products; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, trichloroethane, and tetrachloroethane; methyl acetate and acetic acid Aliphatic alkyl esters such as ethyl; and ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran.
  • thioacetal, acetal or asilal is preferably used because it does not produce free formaldehyde under the reaction conditions and does not substantially produce water by reacting with water produced as a by-product in the reaction.
  • the use of acetals and asylals is preferred.
  • the above-mentioned acid itself is also preferably used as a solvent. These solvents may be used alone or in combination of two or more.
  • These solvents can be used in a range of 0.1 to 100 times, preferably 0.2 to 50 times in weight ratio to the raw material N-substituted carbamic acid-O-monoaryl ester. .
  • the reaction temperature is preferably 10 ° C. to 160 ° C., more preferably 20 to 140 ° C., still more preferably 50 ° C. to 120 ° C.
  • an undesirable side reaction such as hydrolysis may occur.
  • the reaction time varies depending on the reaction method, the compound to be used, and the reaction conditions, it can be carried out in the range of 1 min to 20 hr.
  • reaction solution is sampled, and the reaction is stopped when the amount of reduction of the raw material N-substituted carbamic acid-O-monoaryl ester reaches a certain level by using a known analytical method such as liquid chromatography.
  • a known analytical method such as liquid chromatography.
  • the average molecular weight of the product N-substituted carbamic acid-O-aryl ester reaches a certain level by using a known analysis method such as gel permeation chromatography, for example.
  • the reaction may be stopped.
  • the N-substituted carbamic acid-O-aryl ester obtained by the above method is an N-substituted carbamic acid-O-aryl ester represented by the above formula (150).
  • N-substituted carbamic acid-O-aryl esters considering the ease of handling, particularly the solution viscosity, a compound in which m is 0 among the above-mentioned compounds is preferred. Even if it contains a polynuclear body (that is, a compound in which m is 1 or more in the above formula (150)), there is no problem as long as it does not contradict the purpose of this embodiment.
  • step (F) The N-substituted carbamic acid-O-aryl ester obtained in step (C) is preferably used in step (F).
  • a known method can be used for the removal, and methods such as membrane separation, distillation separation, and crystallization can be used, but distillation separation is preferable.
  • the aromatic hydroxy composition used in the next step (step (F)) is used in the reaction solution of step (C).
  • step (C) is added to form a mixed solution, and the compound remaining in the reaction solution of step (C) (methyleneating agent, reaction solvent, catalyst, etc. used in step (C)) is separated from the mixture by distillation. This is a preferable method because the distillation separation can be carried out without precipitating the N-substituted carbamic acid ester.
  • step (C) since an acid is used, it is necessary to pay attention to the material of the reactor and the condenser. However, as long as the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used. Processes can be added as necessary, and processes and devices in a range that can be assumed by the contractor and the engineer may be added.
  • Route 5) is a method of performing step (R), performing step (C), and performing step (P). Route 5) is also an aspect of the method shown in route 3).
  • the organic primary amine used in the step (A) is an aromatic organic monoprimary amine represented by the following formula (5), and after the step (R), the following step (C ), And at least two molecules of the N-substituted carbamic acid-O—R 2 ester are converted into a methylene group (—CH 2 —) from the N-substituted carbamic acid-O—R 2 ester obtained in step (R).
  • step (P) To obtain an N-substituted carbamic acid-O—R 2 ester, which is then subjected to step (P), wherein the at least two molecules of the N-substituted carbamic acid-O—R 2 ester are converted into the methylene group ( Reacting an N-substituted carbamic acid-O—R 2 ester crosslinked with —CH 2 —) with an aromatic hydroxy composition, the at least two molecules of the N-substituted carbamic acid—O—R 2 ester are rack in - the methylene group (-CH 2) It was a method of obtaining N- substituted carbamic acid -O-R 2 ester and N- substituted carbamate -O- aryl esters derived from aromatic hydroxy composition.
  • At least two molecules of the N-substituted carbamic acid —O— (R 2 or aryl) ester are obtained by crosslinking an aromatic group derived from an aromatic organic monoprimary amine contained in the ester with a methylene group (—CH 2 —).
  • the N-substituted carbamic acid-O-aryl ester in this route 5) is an N-substituted carbamic acid produced in a trace amount when an aromatic hydroxy composition is used in step (A) and / or step (R). O-aryl esters are shown.
  • the organic primary amine is subjected to step (A) using the organic primary amine represented by the formula (5), and the ureido represented by the formula (1) derived from the organic primary amine.
  • step (R) A compound having a group, and then performing step (R) to obtain an N-substituted carbamic acid-O—R 2 ester derived from the compound having the ureido group, and then performing step (C), At least two molecules of the N-substituted carbamic acid-O—R 2 ester are crosslinked with a methylene group (—CH 2 —) to obtain an N-substituted carbamic acid-O—R 2 ester, and then the step (P) is performed.
  • N-substituted carbamic acid-O—R 2 ester bridged with the methylene group (—CH 2 —), the N-substituted carbamic acid-O—R 2 ester derived from an aromatic hydroxy compound and N— Substituted carbamic acid-O-a It is a method to obtain a Ruesuteru.
  • the organic primary amine used in this route is the organic primary amine represented by the formula (5), and the compound having a ureido group obtained in the step (A) of this route is the organic primary amine.
  • —O—R 2 ester more specifically, an N-substituted carbamic acid —O—R 2 ester represented by the following formula (146), which is obtained in step (C) of this route.
  • carbamic acid -O-R 2 ester A N- substituted carbamic acid -O-R 2 ester N- substituted carbamic acid -O-R 2 ester represented by the following formula (151) derived from, obtained in this route step (P) N- substituted
  • the carbamic acid-O-aryl ester is an N-substituted carbamic acid-O-aryl ester represented by the formula (150) derived from the N-substituted carbamic acid-O—R 2 ester and an aromatic hydroxy composition. . Examples of each specific compound are included in the above-described compounds.
  • At least one position in the ortho position and / or para position of the NH 2 group of the aromatic organic monoprimary amine represented by the formula (5) is unsubstituted, and the R 3 to R 6 groups are each aromatic in the ring R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with an aromatic ring.
  • R 3 to R 6 groups may be formed of a hydrogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aryl group having a hydroxy group, a saturated aliphatic bond and / or an ether
  • the total number of carbon atoms constituting the mono primary amine is 6 to 13 It consists of an integer number.
  • the compound having a ureido group obtained in the step (A) is a compound having at least one ureido group represented by the following formula (148).
  • R 3, R 4, R 5 , R 6 groups of formula (148) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5)
  • a compound in which the amino group (—NH 2 group) of the organic primary amine represented by the formula (5) is a ureido group (—NH—CO—NH 2 ).
  • At least one position of the ortho-position and / or para-position of the ureido group of the N-substituted aromatic organic monourea represented by the formula (148) is unsubstituted, and the R 3 to R 6 groups each have aromaticity of the ring R 3 to R 6 groups may each independently substitute an aromatic ring, or R 3 to R 6 groups may be bonded together to form a ring together with the aromatic ring.
  • the R 3 to R 6 groups may be formed of a hydrogen atom or a group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aryl group having a hydroxy group, a saturated aliphatic bond and / or an ether
  • R 3 to R 6 are groups selected from a group composed of a group bonded by a bond, and are groups having an integer range of 0 to 7 carbon atoms, and N— represented by the formula (148) Ureides constituting substituted aromatic organic monoureas The total number of carbon atoms excluding the group (—NH—CO—NH 2 ) is composed of 6 to 13. )
  • the step (A) is carried out, and the N-substituted carbamic acid-O—R 2 ester obtained in the step (R) is at least one N-substituted carbamic acid represented by the following formula (146): O—R 2 ester.
  • the ureido group (—NH—CO—NH 2 ) of the compound having a ureido group represented by the formula (148) becomes a carbamic acid-O—R 2 ester group composed of an R 2 group derived from an alcohol.
  • R 2 to R 6 groups are the groups shown above.
  • the step (R) is carried out, and the N-substituted carbamic acid-O—R 2 ester obtained in the step (C) is at least one N-substituted carbamic acid represented by the following formula (151): O—R 2 ester.
  • R 3, R 4, R 5 , R 6 groups of formula (151) is selected from R 3, R 4, R 5 , R 6 groups of the organic primary amine represented by above formula (5) It is a group.
  • R 2 to R 6 groups are the groups shown above.
  • m is an integer of 0 to 6.
  • Steps (A) and (R) of this route the organic primary amine used is Formula (5), and Step (A), Step (R) and Step (P) of this route are described in Route 4.
  • the step (A) and the step (R) are performed under the same conditions.
  • step (C) of this route is carried out under the conditions of step (C) described in route 4) except that the raw material to be reacted is N-substituted carbamic acid-O—R 2 ester.
  • the raw material used was N-substituted carbamic acid-O-mono (R 2 ester) in route 4), whereas in this route, N-substituted carbamine was used.
  • acid -O-R 2 ester is a methylene group (-CH 2 -) crosslinked with, N- except that a substituted carbamic acid -O-R 2 ester, in the conditions of step (P) described in route 4) carry out.
  • reaction conditions for producing an N-substituted carbamic acid-O—R 2 ester by reacting a compound having a ureido group with an alcohol in step (R) vary depending on the compound to be reacted, but the amount of alcohol used is
  • the stoichiometric ratio with respect to the ureido group of the compound having a ureido group is in the range of 1 to 500 times. If the amount is less than 1 time, a complicatedly substituted carbonyl compound or a high molecular weight compound having a carbonyl bond in the molecule is likely to be formed. Therefore, it is preferable to use a large excess of alcohol. For example, it is preferably in the range of 1 to 200 times, more preferably in the range of 1.5 to 100 times, and still more preferably in the range of 2 to 50 times.
  • the reaction temperature depends on the compound used, but is preferably in the range of 100 ° C to 350 ° C. A temperature lower than 100 ° C. is not preferable because the reaction is slow, the reaction hardly occurs, or the number of complicatedly substituted carbonyl compounds increases. On the other hand, at a temperature higher than 350 ° C., urea (and N-unsubstituted carbamic acid ester) remaining in the step (A) or produced in the system of the step (R) is decomposed or the hydroxy composition is dehydrated. This is not preferable because it may be easily modified or a decomposition reaction or a modification reaction of the N-substituted carbamic acid-O—R 2 ester, which is a product, easily occurs. From such a viewpoint, a more preferable temperature is in the range of 120 ° C. to 320 ° C., further preferably in the range of 140 ° C. to 300 ° C.
  • the reaction for producing the N-substituted carbamic acid-O—R 2 ester is an equilibrium reaction, and the reaction is biased toward the original system. Therefore, by-product ammonia is removed from the system as much as possible. It is preferable to carry out the reaction. Preferably, ammonia is removed so that the ammonia concentration in the reaction solution is 1000 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less, and most preferably 30 ppm or less. Meaning in the liquid phase at the time of implementation).
  • a reactive distillation method, a method using an inert gas, a membrane separation, a method using adsorption separation, and the like can be performed.
  • the reactive distillation method is a method in which ammonia that is sequentially generated under the reaction is separated in a gaseous state by distillation. In order to increase the distillation efficiency of ammonia, it can also be carried out under boiling alcohol, solvent or hydroxy composition.
  • the method using an inert gas is a method in which ammonia that is sequentially generated under reaction is separated from a reaction system by being accompanied by an inert gas in a gaseous state.
  • the inert gas for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane or the like is used alone or in combination, and the inert gas is preferably introduced into the reaction system.
  • Examples of the adsorbent used in the adsorption separation method include adsorbents that can be used under temperature conditions in which the reaction is performed, such as silica, alumina, various zeolites, and diatomaceous earth.
  • the method for removing these ammonia out of the system may be carried out alone or in combination of a plurality of methods.
  • a catalyst can be used for the purpose of increasing the reaction rate.
  • catalysts include basic catalysts such as lithium, sodium, potassium, calcium, barium methylate, ethylate, butyrate (isomers), rare earth elements, antimony, bismuth, and oxides of these elements. , Sulfides and salts, simple boron and boron compounds, copper group, zinc group, aluminum group, carbon group, titanium group metals and their metal oxides and sulfides in the periodic table, carbon other than carbon in the periodic table Group, titanium, vanadium, and chromium group carbides and nitrides are preferably used.
  • the amount used is not particularly limited, but the catalyst can be used in a stoichiometric ratio of 0.0001 to 100 times the ureido group of the compound having a ureido group.
  • the reaction pressure varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 Pa to 10 MPa (absolute pressure), which facilitates industrial implementation. In view of the properties, the range of 0.1 Pa to 5 MPa (absolute pressure) is more preferable, and in view of removing gaseous ammonia out of the system, 0.1 Pa to 1.5 MPa (absolute pressure) is more preferable.
  • the reaction time (residence time in the case of continuous reaction) varies depending on the composition of the reaction system, the reaction temperature, the ammonia removal method, the reaction apparatus, the reaction pressure, etc., but is usually from 0.01 to 100 hours.
  • the reaction time can also be determined by the amount of N-substituted carbamic acid-O—R 2 ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) as the target compound.
  • the reaction solution is sampled, and the content of N-substituted carbamic acid ester (in some cases, the total with N-substituted carbamic acid-O-aryl ester) in the reaction solution is quantified to have a ureido group
  • the reaction may be stopped after confirming that the compound is produced in a yield of 10% or more, or the reaction may be stopped after confirming that the yield is 90% or more.
  • the reaction solution containing the N-substituted carbamic acid-O—R 2 ester obtained in the step (R) is later converted into an N-substituted carbamic acid-O-aryl ester in a step including the step (P).
  • step (F) an isocyanate is obtained.
  • the yield is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more.
  • reaction solvent for example, pentane (each isomer), hexane (each isomer), heptane (each isomer) ), Octane (each isomer), nonane (each isomer), decane (each isomer), and other alkanes; benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (Each isomer), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; nitrile compounds such as acetonitrile and benzonitrile; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer) Body),
  • aromatic compounds substituted by nitro groups polycyclic hydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, dibenzyltoluene (each isomer); cyclohexane, cyclopentane, cyclooctane, ethyl Aliphatic hydrocarbons such as cyclohexane; Ketones such as methyl ethyl ketone and acetophenone; Esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, and benzyl butyl phthalate; Tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether , Ethers such as diphenyl sulfide and thioethers; ketone compounds such as acetone and methyl ethyl ketone; ester
  • the reaction includes a hydroxy composition, a compound having a carbonyl group derived from urea (N-unsubstituted carbamic acid ester, biuret, etc., a compound that inherits the carbonyl group possessed by urea, and N-substituted carbamic acid And a gas phase containing ammonia produced as a by-product in the reaction, and a liquid phase in which the reaction is carried out. Most of the reactions are performed in the liquid phase, but depending on the reaction conditions, the reactions may occur in the gas phase. At that time, the liquid phase volume content in the reactor in which the reaction is carried out is preferably 50% or less.
  • a polymer by-product When the reaction is carried out continuously over a long period of time, a polymer by-product may be generated due to fluctuations in operating conditions (temperature, pressure, etc.), but if the liquid phase volume content in the reactor is large, Such polymeric by-products can be prevented from adhering to and accumulating in the reactor.
  • the liquid phase volume content is too large, the removal efficiency of by-product ammonia is deteriorated and N-substituted carbamic acid-O—R 2 ester (in some cases, N-substituted carbamic acid-O-aryl ester and
  • the liquid phase volume content with respect to the gas phase is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less.
  • the amount is the reaction tank part, in the case of a tower reactor, the stage below the feed stage (not including the tower bottom and reboiler part), and in the thin film distiller, Represents the phase capacity ratio.)
  • the reaction apparatus used for carrying out the reaction is not particularly limited, and a known reactor can be used, but a tank-type and / or tower-type reactor is preferably used.
  • a reactor equipped with a condenser is preferred.
  • the reaction is a system including a gas phase containing a hydroxy composition, a compound having a carbonyl group derived from urea, and ammonia by-produced in the reaction, and a liquid phase for performing the reaction.
  • the liquid phase volume content in the reactor in which the reaction is performed is preferably 50% or less, and the reactor that performs the reaction is also selected to meet the conditions.
  • reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination.
  • a well-known condenser can be used.
  • conventionally known condensers such as a multi-tube cylindrical condenser, a double-pipe condenser, a single-pipe condenser, and an air-cooled condenser can be used in appropriate combination.
  • the condenser may be provided inside the reactor, or may be provided outside the reactor and connected to the reactor by piping.
  • the type of the reactor or condenser, the condensate Considering the handling method, etc. various forms are adopted.
  • the material of the reactor and the condenser and known materials can be used.
  • glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used.
  • SUS304, SUS316, SUS316L, etc. are also inexpensive and can be preferably used.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary.
  • a step of dissolving a compound having a ureido group in an aromatic hydroxy composition a step of dissolving an aromatic hydroxy compound, a step of separating alcohol, a step of separating and / or purifying an aromatic hydroxy compound, and a generated reaction solution
  • Steps and equipment within the range that can be envisaged by the contractor and the engineer such as a step of purifying the N-substituted carbamic acid-O—R 2 ester from the above, a step of incineration or disposal of by-products and the like, may be added.
  • an N-substituted carbamic acid-O—R 2 ester is produced by reacting a compound having a ureido group and an alcohol in a liquid phase using a reactor (equipped with a condenser). It is a process.
  • the gaseous component containing the compound having a carbonyl group derived from urea and ammonia produced as a by-product in the reaction, which is produced in the step (R) is introduced into a condenser provided in the reactor. Then, a part or all of the alcohol and a compound having a carbonyl group derived from urea are condensed, and ammonia is recovered as a gas.
  • the compound having a carbonyl group derived from urea contained in ammonia recovered as a gas from the condenser is set to a specific amount or less. That is, the ratio of the number of carbonyl groups (—C ( ⁇ O) —) contained in the ammonia-containing compound having a carbonyl group derived from urea to the ammonia molecule is 1 or less, preferably 0.8. 5 or less, more preferably 0.1 or less, and still more preferably 0.01 or less.
  • the reason why the amount of the compound having a carbonyl group derived from urea contained in the ammonia is in a specific range is to avoid adhesion and accumulation of solid components in a line for transferring the ammonia from the condenser. It is.
  • solid components adhering and accumulating in the ammonia transfer line can be identified, as a result of studies by the present inventors, it has been found that most of them are compounds having a carbonyl group.
  • a method of avoiding such adhesion and accumulation of solid components a method of decomposing a compound having a carbonyl group by heating a line for transferring ammonia can be considered, but in the study by the present inventors, only heating is performed.
  • decomposition products for example, isocyanic acid
  • the decomposition products react with compounds having other carbonyl groups, so that the adhesion and accumulation of solid components can be completely avoided. was difficult.
  • the compound having a carbonyl group contained in the ammonia or a decomposition product thereof is rapidly generated particularly at the outlet of the line for transferring ammonia (a portion in contact with the atmosphere). It turned out to be solidified by cooling, and the adhesion and accumulation of solid components were often significant.
  • the present inventors have surprisingly found that the compound having a carbonyl group derived from a carbonic acid derivative contained in the ammonia is not more than the specific amount described above, so that a solid is obtained. It has been found that the problem of component adhesion and accumulation can be solved.
  • the present inventors have a compound having a carbonyl group derived from a carbonic acid derivative or a carbonyl group derived from the carbonic acid derivative for adhesion or accumulation to a line. It is assumed that it is caused by the decomposition and / or polymerization product of the compound, and by making the carbonyl group contained in the compound having a carbonyl group derived from the carbonic acid derivative below a specific concentration, the carbonyl derived from the carbonic acid derivative This is considered to be because the adhesion of the group-containing compound itself and the decomposition and / or polymerization reaction rate of the compound are remarkably reduced.
  • the condensed hydroxy composition and the compound having a carbonyl group derived from urea have a stoichiometric amount relative to the compound having the carbonyl group derived from the condensed urea.
  • the stoichiometric ratio is 1 or more, preferably the stoichiometric ratio is 2 or more, more preferably the stoichiometric ratio is 3 or more.
  • the reason for this range is that the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea that is condensed in the condenser can be a uniform liquid mixture. This not only facilitates handling of the mixture, but also avoids problems such as adhesion and accumulation of solid components on the condenser.
  • the mixture of the hydroxy composition and the compound having a carbonyl group derived from urea condensed in the condenser in step (R) is circulated inside the reactor to react in the reaction of step (A). May be reused.
  • the amount of ammonia contained in the mixture is preferably 5000 ppm or less, more preferably 3000 ppm or less, and still more preferably 2000 ppm or less.
  • step (C) of this route at least one N-substituted carbamic acid —O—R 2 ester (containing a reaction solution) obtained in step (R) is crosslinked with a methylene group (—CH 2 —).
  • step (C) at least two molecules of the N-substituted carbamic acid-O—R 2 ester are crosslinked with the methylene group (—CH 2 —) to obtain an N-substituted carbamic acid-O—R 2 ester.
  • step (C) at least one molecule of the N-substituted carbamic acid-O—R 2 ester represented by the above formula (151) was crosslinked with a methylene group (—CH 2 —).
  • N-substituted carbamic acid-O—R 2 ester is obtained.
  • the aromatic hydroxy compound constituting the aromatic hydroxy composition used in the step (A) and / or the step (R) is represented by the formula (2).
  • the aromatic hydroxy compound represented by formula (7) is preferred, and the aromatic hydroxy compound represented by formula (7) is more preferred.
  • it is an aromatic hydroxy compound represented by the formula (31), or naphthol (each isomer), phenoxyphenol (each isomer), diphenoxy-phenol (each isomer), and the ortho position of the hydroxy group or R 19 to R of the aromatic hydroxy compound represented by the formula (31) are naphthol (each isomer), phenoxyphenol (each isomer), and diphenoxy-phenol (each isomer) which are unsubstituted at the para-position.
  • 23 is an aromatic monohydroxy compound in which 23 groups are linear and / or cyclic saturated alkyl groups.
  • the aromatic hydroxy compound constituting the aromatic hydroxy composition used in the step (P) of route 5) is preferably an active aromatic hydroxy compound, and is selected from the aromatic hydroxy compounds represented by the formula (32).
  • Ring A is a group derived from an aromatic hydroxy compound constituting the aromatic hydroxy composition as defined above, and is a group of hydroxyl groups directly bonded to the aromatic hydrocarbon ring from the aromatic hydroxy compound. Represents a residue with one hydrogen atom removed,
  • the R 3 to R 6 groups represent the groups defined above; m is an integer of 0 to 6.
  • step (C) The N-substituted carbamic acid-O—R 2 ester obtained in step (R) of route 5) is often referred to as N-substituted carbamic acid-O-mono (R 2 ester) or N-substituted carbamic acid mono-R 2 ester. .
  • the step (C) can be carried out by a known method (for example, refer to German Patent No. 1042891). If an aromatic hydroxy composition is used in step (R) before carrying out step (C), it is separated from the resulting reaction solution containing the N-substituted carbamic acid-O—R 2 ester.
  • the step (C) may be performed in the presence of an aromatic hydroxy compound
  • the aromatic hydroxy compound may also be cross-linked with a methyleneated cross-linking agent to produce a by-product such as a polyaromatic hydroxy compound.
  • the amount of the methyleneated cross-linking agent used may be increased, so that the aromatic hydroxy compound is preferably separated.
  • a known method can be used for the separation, and it varies depending on the compound to be used. However, the separation is performed by distillation or by using the difference in solubility between the N-substituted carbamic acid-O—R 2 ester and the aromatic hydroxy compound for separation.
  • N-substituted carbamic acid-O—R 2 ester and the aromatic hydroxy compound can be solidified and filtered. Since these methods depend on the physical properties of each compound to be used, they are not specifically shown, but methods, conditions, and the like can be sufficiently selected within the scope of knowledge of those skilled in the art.
  • the amount of the aromatic hydroxy compound after the separation operation is less than 1 time, preferably 0. 0, in stoichiometric amount with respect to the N-substituted carbamic acid-O—R 2 ester. Remove until 5 times, more preferably 0.1 times aromatic hydroxy compound is present. At this time, it may be removed in the presence of a solvent used in the step (C) described later.
  • Examples of the methyleneated cross-linking agent preferably used in the step (C) include formaldehyde, paraformaldehyde, trioxane, dialkoxymethane having a lower alkyl group having 1 to 6 carbon atoms (for example, dimethoxymethane, diethoxymethane, dioxane). And diacyloxymethane having a lower carboxyl group such as propoxymethane, dipentanoxymethane, dihexyloxymethane), diacetoxymethane, and dipropoxymethane. These may be used alone or in combination of two or more.
  • an aqueous formaldehyde solution is particularly preferable when it is industrially implemented or considering the ease of handling of the methyleneated crosslinking agent.
  • the ratio of the N-substituted carbamic acid-O-mono (R 2 ester) to the methyleneated crosslinker is not particularly limited, but relative to the methyleneated crosslinker
  • the N-substituted carbamic acid-O-mono (R 2 ester) is preferably used in a stoichiometric ratio of 2 to 20 times.
  • N-substituted carbamic acid-O-mono (R 2 ester) The larger the amount of N-substituted carbamic acid-O-mono (R 2 ester) used, the more the polynuclear body (the polynuclear body here means three or more aromatic rings (aromatic rings derived from organic primary amines)) Represents an N-substituted carbamic acid-O—R 2 ester bonded by a methylene bridge structure, that is, a compound in which m is an integer of 1 or more in the above formula (151). On the other hand, if too much N-substituted carbamic acid-O-mono (R 2 ester) is used, the residual amount of raw material N-substituted carbamic acid-O-mono (R 2 ester) may increase. Many.
  • the amount of N-substituted carbamic acid-O-mono (R 2 ester) used is preferably in the range of 3 to 15 times, more preferably 5 to 10 times the stoichiometric ratio with respect to the methyleneated crosslinking agent. It is a range.
  • an acid catalyst as a catalyst.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, and organic acids such as formic acid, acetic acid, oxalic acid and toluenesulfonic acid.
  • acids called super strong acids such as hydrobromic acid, perchloric acid, chlorosulfonic acid, and trifluoromethanesulfonic acid are also effective.
  • ion exchange resins having acidic groups such as carboxyl groups and sulfonic acid groups
  • acids called Lewis acids such as trifluoroboric acid, iron chloride, aluminum chloride, zinc chloride, and titanium chloride. .
  • These acids are used in a stoichiometric ratio of 0.001 to 10 with respect to the raw material N-substituted carbamic acid ester in the case of the above-mentioned protonic acids such as inorganic acids, organic acids, and super strong acids.
  • the range is preferably 0.01 to 5.
  • these acids when used as an aqueous solution, they can be used at a concentration in the range of 10 to 95 wt%, preferably in the range of 20 to 80 wt%, with respect to the water in the reaction system. When the concentration is lower than 10 wt%, the reaction rate of the condensation reaction is extremely slow. When the concentration is higher than 95 wt%, undesirable side reactions such as hydrolysis of the raw material may occur.
  • the condensation reaction can be carried out without solvent or in the presence of a solvent.
  • the solvent preferably used include linear, branched, and cyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, hexadecane, cyclopentane, and cyclohexane; benzene, toluene, xylene And their aromatic, halogen, nitro group-substituted products; halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane; methyl acetate, acetic acid Aliphatic alkyl esters such as ethyl; and ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran.
  • thioacetal, acetal or asilal is preferably used because it does not produce free formaldehyde under the reaction conditions and does not substantially produce water by reacting with water produced as a by-product in the reaction.
  • the use of acetals and asylals is preferred.
  • the above-mentioned acid itself is also preferably used as a solvent. These solvents may be used alone or in combination of two or more. These solvents are used in a weight ratio of 0.1 to 100 times, preferably 0.2 to 50 times, relative to the raw material N-substituted carbamic acid-O-mono (R 2 ester). be able to.
  • the reaction temperature is preferably 10 ° C. to 160 ° C., more preferably 20 to 140 ° C., still more preferably 50 ° C. to 120 ° C.
  • an undesirable side reaction such as hydrolysis may occur.
  • the reaction time varies depending on the reaction method, the compound to be used, and the reaction conditions, it can be carried out in the range of 1 min to 20 hr.
  • reaction solution is sampled, and when the amount of reduction of the raw material N-substituted carbamic acid-O-mono (R 2 ester) reaches a certain level using a known analysis method such as liquid chromatography, for example.
  • the reaction may be stopped, or the average molecular weight of the product N-substituted carbamic acid-O-aryl ester reaches a certain level by using a known analysis method such as gel permeation chromatography. At this point, the reaction may be stopped.
  • N- substituted carbamic acid -O-R 2 ester obtained by the above method is a N- substituted carbamic acid -O-R 2 ester represented by the formula (151).
  • N-substituted carbamic acid-O—R 2 esters in view of ease of handling, particularly solution viscosity, a compound in which m is 0 among the above-mentioned compounds is preferred. In other words, there is no problem as long as it is not contrary to the gist of the present embodiment.
  • the N-substituted carbamic acid-O—R 2 ester obtained in step (C) is preferably used in step (P). You may remove the compound (The methyleneating agent, the reaction solvent, the catalyst, etc.
  • step (C) A known method can be used for the removal, and methods such as membrane separation, distillation separation, and crystallization can be used, but distillation separation is preferable.
  • the aromatic hydroxy composition used in the next step (step (P)) is added to the reaction solution of step (C). Is added to form a mixed solution, and the compound remaining in the reaction solution of step (C) (methyleneating agent, reaction solvent, catalyst, etc. used in step (C)) is separated from the mixture by distillation.
  • step (C) since an acid is used, it is necessary to pay attention to the material of the reactor and the condenser. However, as long as the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • the compound used in step (C) does not cause a problem such as corrosion, it is particularly limited.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used. Processes can be added as necessary, and processes and devices in a range that can be assumed by the contractor and the engineer may be added.
  • Step (P) Transesterification Step Since this step is a step of converting the ester group of the N-substituted carbamic acid-O—R 2 ester, it is also referred to as “transesterification step” in the present embodiment.
  • an aromatic hydroxy composition a composition containing at least one aromatic hydroxy compound represented by the following formula (2)
  • FIG. 6 is a conceptual diagram showing the step (P).
  • step (P) an alcohol derived from N-substituted carbamic acid-O—R 2 ester is generated.
  • step (P) will be described.
  • the aromatic hydroxy compound in the aromatic hydroxy composition to be reacted is represented by the above formula (2), formula (7), formula (31), formula (32), formula (38), formula (39), formula (40). Any of the aromatic hydroxy compounds represented by the above may be used.
  • the aromatic hydroxy compound represented by the formula (7) or the formula (31) is contained, and more preferably, an aromatic hydroxy composition containing the active aromatic hydroxy compound represented by the formula (32) is used. More preferably, an aromatic hydroxy composition containing an active aromatic hydroxy compound represented by formula (38) is used.
  • step (P) various methods can be performed according to the compound to be used with reference to known methods (for example, refer to WO2008 / 059953).
  • the reaction conditions in the step (P) vary depending on the compound to be reacted, but the aromatic hydroxy compound in the aromatic hydroxy composition is added to the ester group constituting the raw material N-substituted carbamic acid-O—R 2 ester. Expressed in stoichiometric ratio, it is used in the range of 2 to 1000 times.
  • the aromatic hydroxy compound is preferably in an excess amount with respect to the ester group constituting the N-substituted carbamic acid-O—R 2 ester of the raw material. In consideration, it is preferably in the range of 2 to 100 times, more preferably in the range of 5 to 50 times.
  • the reaction temperature is usually in the range of 100 ° C. to 300 ° C., and a high temperature is preferable for increasing the reaction rate. On the other hand, a side reaction tends to occur at a high temperature, and preferably 150 ° C. to 250 ° C. It is in the range of ° C.
  • a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually in the range of 20 to 1 ⁇ 10 6 Pa.
  • the reaction time (retention time in the case of a continuous process) is not particularly limited, and is usually 0.001 to 100 hours, preferably 0.01 to 50 hours, more preferably 0.1 to 30 hours.
  • the reaction solution can be collected and the reaction can be terminated after confirming that the desired amount of the desired N-substituted carbamic acid-O-aryl ester has been formed by, for example, liquid chromatography.
  • a catalyst is not always necessary, but there is no problem in using the catalyst in order to lower the reaction temperature or complete the reaction at an early stage.
  • the catalyst is used in an amount of 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the weight of the N-substituted carbamic acid-O—R 2 ester.
  • the catalyst examples include Lewis acids and Lewis Transition metal compounds that generate acids, organotin compounds, copper group metals, zinc, iron group metal compounds, specifically, AlX 3 , TiX 3 , TiX 4 , VOX 3 , VX 5 , ZnX 2 , FeX 3 , A Lewis acid represented by SnX 4 (where X is a halogen, an acetoxy group, an alkoxy group, an aryloxy group) and a transition metal compound that generates a Lewis acid; (CH 3 ) 3 SnOCOCH 3 , (C 2 H 5 ) SnOCOC 6 H 5, Bu 3 SnOCOCH 3, Ph 3 SnOCOCH 3, Bu 2 Sn (OCOCH 3) 2, Bu 2 Sn (OCOC 11 H 23 2, Ph 3 SnOCH 3, ( C 2 H 5) 3 SnOPh, Bu 2 Sn (OCH 3) 2, Bu 2 Sn (OC 2 H 5) 2, Bu 2 Sn (OPh) 2, Ph 2 Sn (CH 3 ) 2 , (
  • an appropriate inert solvent such as hexane (each isomer), heptane (each isomer), for example, for the purpose of facilitating the reaction operation, Alkanes such as octane (each isomer), nonane (each isomer), decane (each isomer); benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each Isomers), aromatic hydrocarbons such as naphthalene and alkyl-substituted aromatic hydrocarbons; chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer), chloronaphthalene, bromonaphthalene, nitrobenzene, nitro Aromatic compounds
  • the transesterification reaction in the present embodiment is an equilibrium reaction. Therefore, in order to perform transesterification efficiently, it is preferable to proceed the reaction while removing the product alcohol (alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester) from the reaction system. Therefore, the aromatic hydroxy compound is selected so that the standard boiling point of the aromatic hydroxy compound used in the transesterification is higher than the standard boiling point of the alcohol derived from the N-substituted carbamic acid-O—R 2 ester of the raw material.
  • the compound having the lowest standard boiling point in the reaction system becomes an alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester, and the product can be easily removed from the reaction system.
  • the two components to be separated have a normal boiling point of 10 ° C. or more and can be distilled and separated industrially, the most in the aromatic hydroxy composition is higher than the normal boiling point of the alcohol. It is preferable to use an aromatic hydroxy compound having a low boiling point (compared with the normal boiling point) and having a standard boiling point of 10 ° C. or higher.
  • transesterification is preferably performed by a continuous method. That is, a raw material N-substituted carbamic acid-O—R 2 ester and an aromatic hydroxy composition are continuously supplied to a reactor to perform transesterification to produce a raw material N-substituted carbamic acid-O.
  • the alcohol derived from —R 2 ester is removed from the reactor as a gas component, and the resulting reaction solution containing the N-substituted carbamic acid-O-aryl ester and the aromatic hydroxy composition is continuously removed from the bottom of the reactor. .
  • the material of the reactor and line for performing the transesterification may be any known material as long as it does not adversely affect the starting materials and the reactants.
  • SUS304, SUS316, SUS316L, etc. are inexpensive and preferably used. it can.
  • instrumentation equipment such as flow meters and thermometers, and known process equipment such as reboilers, pumps, condensers, etc. may be added.
  • a known method such as cooling water or brine can be used.
  • a process may be added as necessary.
  • a step of dissolving an aromatic hydroxy compound For example, a step of dissolving an aromatic hydroxy compound, a step of separating an alcohol, a step of separating and / or purifying an aromatic hydroxy compound, a step of purifying an N-substituted carbamic acid-O-aryl ester from the produced reaction solution, You may add the process and apparatus of the range which the said contractor and the said engineer can assume, such as the process of incinerating or discarding a by-product.
  • limiting in particular in the form of a reactor A well-known tank-like and tower-like reactor can be used.
  • stirring tank for example, stirring tank, multistage stirring tank, distillation tower, multistage distillation tower, multitubular reactor, continuous multistage distillation tower, packed tower, thin film evaporator, reactor with support inside, forced circulation reactor, falling film
  • a method using a reactor including any of an evaporator, a drop evaporator, a trickle phase reactor, and a bubble column, and a combination of these may be used.
  • a method using a thin film evaporator or a columnar reactor is preferred, and it is derived from the raw material N-substituted carbamic acid-O—R 2 ester to be produced.
  • the multi-stage distillation column is a distillation column having a multi-stage of two or more theoretical distillation stages, and any column can be used as long as continuous distillation is possible.
  • Examples of such a multi-stage distillation column include a tray column type using a bubble tray, a perforated plate tray, a valve tray, a counter-flow tray, etc., a Raschig ring, a lessing ring, a pole ring, a Berle saddle, an interlocks.
  • Any of those usually used as a multistage distillation column can be used, such as a packed column type packed with various packings such as saddle, Dixon packing, McMahon packing, helipak, sulzer packing, and melapack.
  • Any packed tower can be used as long as it is a packed tower in which the above-mentioned known filler is packed in the tower.
  • a shelf-packed mixing type having both a shelf portion and a portion filled with a packing is also preferably used.
  • a line for supplying an inert gas and / or a liquid inert solvent from the bottom of the reactor may be separately attached, or a mixture containing the target N-substituted carbamic acid-O-aryl ester and an aromatic hydroxy compound
  • the liquid contains a raw material N-substituted carbamic acid-O—R 2 ester
  • a line for circulating part or all of the mixed liquid to the reactor may be attached.
  • this inert solvent may be gaseous and / or liquid.
  • the gaseous component containing the alcohol derived from the raw material N-substituted carbamic acid-O—R 2 ester extracted from the reactor is preferably purified using a known method such as a distillation column to obtain the steps (A) and / or Or it can recycle
  • step (F) of obtaining an isocyanate by thermally decomposing the N-substituted carbamic acid-O-aryl ester obtained in the routes 1) to 5) will be described.
  • N-substituted carbamic acid-O-aryl ester is thermally decomposed in the following step (F), and is represented by the following formula (6) derived from the N-substituted carbamic acid-O-aryl ester.
  • R 1 is an organic group containing an integer number of carbon atoms in the range of 1 to 85, and represents an organic group substituted with s NCO groups, and s is an integer of 1 to 10.
  • the N-substituted carbamic acid-O-aryl ester produced by the above method is preferably used for the production of isocyanate.
  • process (F) a process for producing an isocyanate by subjecting the N-substituted carbamic acid-O-aryl ester to a thermal decomposition reaction
  • a solvent may or may not be used, but it is preferably carried out in the presence of an aromatic hydroxy composition.
  • the aromatic hydroxy composition is used in carrying out step (B) or step (P), and therefore the step (( F) may be carried out, and if necessary, the amount of the aromatic hydroxy composition may be adjusted and step (F) may be carried out.
  • Step (F) since the aromatic hydroxy composition is separated in Step (C), Step (F) may be carried out again using the separated aromatic hydroxy composition. Or the quantity of the aromatic hydroxy composition to be used may be adjusted, and an aromatic hydroxy composition may be newly adjusted and used.
  • the solvent used in the step (C) may be separated from the N-substituted carbamic acid-O-aryl ester or may be used together with the aromatic hydroxy composition.
  • the amount of the aromatic hydroxy composition is adjusted or newly adjusted, but the amount depends on the transfer efficiency of the N-substituted carbamic acid-O-aryl ester and the storage tank during storage.
  • the number of aromatic hydroxy compounds in the aromatic hydroxy composition is 0 with respect to the total number of ester groups of —O-aryl ester contained in the N-substituted carbamic acid-O-aryl ester. 2 to 50, preferably 0.3 to 30, and more preferably 1 to 20.
  • suitable inert solvents for the purpose of facilitating the reaction operation, for example, hexane (each isomer), heptane (each isomer), octane (each isomer), Nonane (each isomer), decane (each isomer) and other alkanes; benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each isomer), naphthalene, etc.
  • suitable inert solvents for the purpose of facilitating the reaction operation, for example, hexane (each isomer), heptane (each isomer), octane (each isomer), Nonane (each isomer), decane (each isomer) and other alkanes; benzene, toluene, xylene (
  • the reaction temperature of the thermal decomposition reaction carried out in the step (F) is usually in the range of 100 ° C. to 300 ° C., and a high temperature is preferable for increasing the reaction rate. Since the side reaction as described above may be caused by the Ar ester and / or the product isocyanate, it is preferably in the range of 150 ° C. to 250 ° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually in the range of 20 to 1 ⁇ 10 6 Pa.
  • the reaction time (retention time in the case of a continuous method) is not particularly limited, and is usually 0.001 to 100 hours, preferably 0.005 to 50 hours, more preferably 0.01 to 10 hours.
  • a catalyst is preferably not used.
  • the catalyst residue or the like is decomposed into the thermal decomposition. Although it may be supplied to the process, such a catalyst residue or the like may be present.
  • N-substituted carbamic acid-O-aryl ester When N-substituted carbamic acid-O-aryl ester is kept for a long time at high temperature, for example, a urea bond-containing compound is formed by decarboxylation reaction from two molecules of N-substituted carbamic acid-O-aryl ester. In some cases, side reactions such as a reaction to form an allophanate group by a reaction with an isocyanate group produced by thermal decomposition of the N-substituted carbamic acid-O-aryl ester may occur. Therefore, the time during which the N-substituted carbamic acid-O-aryl ester and the isocyanate are maintained at a high temperature is preferably as short as possible.
  • the thermal decomposition reaction is preferably performed by a continuous method.
  • a mixture containing the N-substituted carbamic acid-O-aryl ester is continuously fed to a reactor, subjected to a thermal decomposition reaction, and the resulting isocyanate and aromatic hydroxy compound are converted into the This is a method of continuously extracting from the pyrolysis reactor.
  • the low boiling point component produced by the pyrolysis reaction of urethane is preferably recovered from the top of the pyrolysis reactor as a gas phase component, and the rest as a liquid phase component from the bottom of the pyrolysis reactor. Collected.
  • the term “low-boiling component produced by thermal decomposition reaction of N-substituted carbamic acid-O-aryl ester” used in the present embodiment refers to thermal decomposition reaction of N-substituted carbamic acid-O-aryl ester.
  • Aromatic hydroxy compounds and / or isocyanates produced by ## STR3 ## correspond to compounds that can exist as gases, particularly under the conditions under which the thermal decomposition reaction is carried out.
  • a method of recovering the liquid phase component containing N-substituted carbamic acid-O-aryl ester by recovering isocyanate and aromatic hydroxy compound produced by the thermal decomposition reaction as gas phase components can be employed.
  • the isocyanate and the aromatic hydroxy compound may be recovered separately in a thermal decomposition reactor.
  • the recovered gas phase component containing the isocyanate is preferably supplied in a gas phase to a distillation apparatus for purifying and separating the isocyanate.
  • the vapor phase component containing the recovered isocyanate can be supplied to the distillation apparatus after it is converted into a liquid phase by a condenser or the like, but the apparatus is often complicated and the energy used is often large, which is preferable. Absent.
  • the liquid phase component contains an N-substituted carbamic acid-O-aryl ester
  • a part or all of the liquid phase component is fed to the top of the pyrolysis reactor, and the N- The substituted carbamic acid-O-aryl ester is again subjected to a thermal decomposition reaction.
  • the upper part of the pyrolysis reactor as used herein means, for example, when the pyrolysis reactor is a distillation column, it indicates the theoretical plate number that is at least the second stage above the tower bottom, and the pyrolysis reactor is a thin film. In the case of a distiller, it refers to the part above the heated surface part.
  • the liquid phase component is preferably 50 ° C. to 180 ° C., more preferably 70 ° C. to 170 ° C., still more preferably, Transfer while keeping at 100 ° C to 150 ° C.
  • the isocyanate and aromatic hydroxy compound produced by the thermal decomposition reaction are recovered as gas phase components, and the liquid phase component containing the N-substituted carbamic acid-O-aryl ester is recovered from the bottom of the thermal decomposition reactor.
  • the method to do can be adopted.
  • the recovered gaseous component containing the isocyanate is preferably supplied in a gas phase to a distillation apparatus for producing and separating the isocyanate.
  • the liquid phase component containing the N-substituted carbamic acid-O-aryl ester is partially or entirely supplied to the upper part of the thermal decomposition reactor, and the N-substituted carbamic acid-O-aryl ester is supplied.
  • the liquid phase component is preferably 50 ° C. to 180 ° C., more preferably 70 ° C. to 170 ° C., still more preferably, Transfer while keeping at 100 ° C to 150 ° C.
  • the aromatic hydroxy compound is recovered as a gas phase component, and the mixture containing the isocyanate is used as a liquid phase component, and the bottom of the thermal decomposition reactor A more recovering method can be adopted.
  • the liquid phase component is supplied to a distillation apparatus to recover the isocyanate.
  • the liquid phase component contains an N-substituted carbamic acid-O-aryl ester
  • the mixture containing the N-substituted carbamic acid-O-aryl ester partially or entirely
  • the N-substituted carbamic acid-O-aryl ester is supplied to the upper part of the thermal decomposition reactor and again subjected to a thermal decomposition reaction.
  • the liquid phase component is preferably 50 ° C. to 180 ° C., more preferably 70 ° C. to 170 ° C., still more preferably, Transfer while keeping at 100 ° C to 150 ° C.
  • the liquid phase component As described above, in the pyrolysis reaction, it is preferable to recover the liquid phase component from the bottom of the pyrolysis reactor. It is a polymeric by-product produced by side reactions caused by N-substituted carbamic acid-O-aryl esters and / or isocyanates, as described above, by having a liquid phase component present in the pyrolysis reactor. This is because it can be dissolved and discharged from the pyrolysis reactor as a liquid phase component, thereby reducing the adhesion and accumulation of the polymeric compound to the pyrolysis reactor.
  • N-substituted carbamic acid-O-aryl ester When N-substituted carbamic acid-O-aryl ester is contained in the liquid phase component, a part or all of the liquid phase component is supplied to the upper part of the pyrolysis reactor, and the N-substituted carbamic acid is supplied.
  • the —O-aryl ester is again subjected to a thermal decomposition reaction.
  • a polymeric by-product may be accumulated in the liquid phase component. In that case, some or all of the liquid phase components can be removed from the reaction system to reduce the accumulation of polymeric by-products or to maintain a constant concentration.
  • a well-known distillation apparatus is used.
  • Various known methods such as a method using a reactor including any of the reactors, a method using a combination thereof, and the like are used.
  • a method using a reactor such as a tubular reactor, more preferably a tubular thin film evaporator, a tubular falling film evaporator, etc.
  • a structure having a large gas-liquid contact area that can be quickly moved to the gas phase is preferable.
  • the material of the pyrolysis reactor and the line may be any known material as long as it does not adversely affect the urethane, the product aromatic hydroxy compound, isocyanate, etc., but SUS304, SUS316, SUS316L, etc. Is inexpensive and can be used preferably.
  • the aromatic hydroxy compound contained in the gas phase component and / or liquid phase component obtained in the above thermal decomposition reaction can be separated and recovered and reused.
  • the aromatic hydroxy compound can be reused as the aromatic hydroxy compound used in step (A) and / or step (B) and / or step (R) and / or step (P).
  • the aromatic hydroxy composition obtained in the step (F) is separated from the isocyanate, and the step (A) and / or the step (B) described in the route 1) or the step (A) described in the route 3) and It is preferable to recycle and / or use the process (R) and / or the process (P).
  • step (F) the unreacted N-substituted carbamic acid-O-aryl ester that was not thermally decomposed in the step (F) is converted into the above-mentioned step (A) and / or step (B) and / or step (R) and / or Or it is a preferable aspect to recycle and use to process (P) and / or process (F).
  • the inside (particularly the wall surface) of the corresponding reactor can be washed with an acid that is a good solvent for the polymer side reaction product, thereby keeping the inside of the reactor clean.
  • the washing acid is not particularly limited as long as it dissolves the polymer by-product, and either an organic acid or an inorganic acid may be used, but an organic acid is preferably used.
  • organic acids include carboxylic acids, sulfonic acids, sulfinic acids, phenols, enols, thiophenols, imides, oximes, aromatic sulfonamides, etc., but preferably carboxylic acids, phenols Kind is used.
  • Such compounds include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, isovaleric acid, 2-methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid, 2-ethylbutanoic acid, 2,2 -Dimethylbutanoic acid, heptanoic acid (each isomer), octanoic acid (each isomer), nonanoic acid (each isomer), decanoic acid (each isomer), undecanoic acid (each isomer), dodecanoic acid (each isomer) ), Tetradecanoic acid (each isomer), hexadecanoic acid (each isomer), acrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, methacrylic acid, angelic acid, tiglic acid, allyl acetic acid, undecenoic acid
  • Saturated or unsaturated aliphatic dicarboxylic acid 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, 2,3-dimethylbutane-1,2,3-tricarboxylic acid, etc.
  • Aromatic carboxylic acid compounds such as isomers
  • aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid, terephthalic acid and methyl isophthalic acid (each isomer)
  • Aromatic tricarboxylic acid compounds such as lithic acid, trimellitic acid, trimesic acid, phenol, methylphenol (each isomer), ethylphenol (each isomer), propylphenol (each isomer), butylphenol (each isomer), pentyl Phenol (each isomer), hexylphenol (each isomer), heptylphenol (each
  • an aromatic hydroxy compound in consideration of the effect when the cleaning solvent remains after the cleaning operation of the thermal decomposition reactor, more preferably an aromatic hydroxy compound, more preferably the N-substitution of the present embodiment. It is the same type of compound as the aromatic hydroxy compound produced by the method for producing carbamic acid-O-aryl ester and / or the thermal decomposition reaction of N-substituted carbamic acid-O-aryl ester.
  • the standard boiling point of the aromatic hydroxy compound is an isocyanate produced by the thermal decomposition reaction of the aforementioned N-substituted carbamic acid-O-aryl ester from the viewpoint of the washing effect. It is preferable to have a boiling point difference of 10 ° C. or more from the normal boiling point of
  • a method of cleaning the reactor using the above-mentioned cleaning solvent a method of cleaning the reactor by introducing the cleaning solvent from the top of the reactor, a cleaning solvent is introduced into the bottom of the reactor, and the cleaning solvent is put into the reactor.
  • Various methods can be used such as a method of cooking and washing the inside.
  • the washing operation does not need to be performed every time the reaction is carried out, and can be arbitrarily determined depending on the compound to be used, the operation rate, etc.
  • the cleaning operation can be performed once a day to once a year, more preferably once a month to a year.
  • the reactor may comprise a line for introducing a cleaning solvent.
  • Step (D), step (E), and step (G) described below may be additionally performed in the above-described method.
  • the step (A) when producing a compound having a ureido group, it is preferable to use an excessive amount of urea relative to the organic primary amine.
  • an excessive amount of unreacted urea exists in the step (B), the step (R) or the step (P) while containing an excessive amount of urea, a compound having a ureylene group is by-produced.
  • the urea is separated by distillation or sublimation.
  • a known method can be used for the separation, and depending on the compound used, methods such as filtration, distillation, and sublimation can be used.
  • the method is performed simultaneously with the step (B), the step (R) or the step (P).
  • the hydroxy composition (the hydroxy composition is at least an aromatic hydroxy composition and / or an aromatic hydroxy compound and / or an alcohol). 1), a gas containing urea-derived carbonyl group-containing compound and ammonia by-produced in the reaction is introduced into the condenser provided in the reaction, and one of the hydroxy compositions Part or all and a compound having a carbonyl group derived from a carbonic acid derivative are condensed.
  • the condensed hydroxy composition has a stoichiometric ratio of 1 or more with respect to the condensed urea and the compound having a carbonyl group derived from urea.
  • the “compound having a carbonyl group derived from urea” condensed in a condenser is a group having a carbonyl group derived from urea used in the reaction between an organic amine, urea and a hydroxy composition.
  • urea itself used as a raw material (unreacted substance and / or excess when used excessively with respect to the organic amine), a compound in which the urea and the hydroxy composition are reacted, the same or different A compound reacted with a carbonic acid derivative is included.
  • specific compounds include urea compounds such as isocyanic acid, urea, biuret, and nurate, and ester groups derived from the hydroxy composition. N-unsubstituted carbamic acid-O-ester which is a group, and carbonate ester whose ester group is a group derived from a hydroxy composition.
  • a compound having a carbonyl group derived from a carbonic acid derivative should be quantified by a method of detecting a carbonyl group contained in the compound by a method such as infrared spectroscopy, near infrared spectroscopy, Raman spectroscopy, or ultraviolet spectroscopy. It can also be quantified by a method of specifically analyzing the produced compound by methods such as gas chromatography, liquid chromatography, and NMR. Many of these compounds having a carbonyl group derived from urea have a high melting point and tend to precipitate. Of the above-mentioned compounds having a carbonyl group derived from urea, urea is particularly important since it has a large production amount (detected amount) and a melting point of 135 ° C.
  • the hydroxy composition to be condensed is set to a stoichiometric ratio of 1 or more with respect to the compound having a carbonyl group derived from the urea to be condensed.
  • a uniform liquid mixture can be obtained. Therefore, not only the handling of the mixture becomes easy, but also problems such as adhesion and accumulation of solid components on the condenser can be avoided. Further, as will be described later, it is also effective to make the compound having a carbonyl group derived from urea contained in ammonia recovered from the condenser below a specific amount.
  • the amount of the hydroxy composition to be condensed with respect to the compound having a carbonyl group derived from the condensed urea is more preferably 2 or more in a stoichiometric ratio, and further preferably 3 or more in a stoichiometric ratio.
  • the condenser is preferably 90.degree. Above the normal boiling point of the hydroxy composition. It is kept at a temperature lower than °C.
  • an N-substituted carbamic acid-O-aryl ester can be produced using an aromatic hydroxy composition containing a plurality of types of aromatic hydroxy compounds.
  • step (D) is performed in route 1) or route 2), in order to recover urea and the compound having a carbonyl group derived from urea as a uniform solution, an aromatic hydroxy composition, urea And the gas containing the compound which has a carbonyl group derived from urea is condensed with a condenser.
  • the aromatic hydroxy composition contains an aromatic hydroxy compound that is easily vaporized to some extent under the reaction conditions.
  • a compound having a ureido group and an aromatic hydroxy composition react mainly in a liquid phase to produce an N-substituted carbamic acid-O-aryl ester. Therefore, the aromatic hydroxy composition is a liquid under reaction conditions. It preferably contains an aromatic hydroxy compound present. Therefore, as the aromatic hydroxy composition, those containing a plurality of types of aromatic hydroxy compounds having different standard boiling points can be preferably used.
  • the aromatic hydroxy compound when the aromatic hydroxy compound is selected so that the normal boiling point of the active aromatic hydroxy compound is the highest in the aromatic hydroxy composition, the formation of N-substituted carbamic acid-O-aryl ester is mainly performed. In the liquid phase where the reaction takes place, the concentration of the active aromatic hydroxy compound is increased, and N-substituted carbamic acid-O-ester derived from the active aromatic hydroxy compound can be produced with higher selectivity. it can.
  • An inert aromatic hydroxy compound having a normal boiling point lower than that of the active aromatic hydroxy compound is preferably introduced into the condenser as a gas phase component, together with a compound having a carbonyl group derived from a carbonic acid derivative, in the condenser. Condensed.
  • FIG. 7 shows an aromatic hydroxy composition containing a plurality of aromatic hydroxy compounds as described above (here, for the sake of simplicity, two types of active aromatic hydroxy compounds and inactive aromatic hydroxy compounds are used.
  • FIG. 2 is a conceptual diagram of a method for producing an N-substituted carbamic acid ester using an aromatic hydroxy compound containing an aromatic hydroxy compound).
  • an active aromatic hydroxy compound examples include the aromatic hydroxy compound represented by the formula (32), preferably the aromatic hydroxy compound represented by the formula (38).
  • the aromatic hydroxy compound shown by Formula (39) is mentioned, More preferably, it is an aromatic hydroxy compound shown by Formula (40).
  • the difference between the standard boiling points of the active aromatic hydroxy compound and the inactive aromatic hydroxy compound described above is generally difficult to define the separability, but the standard boiling point of the two components to be separated is usually 10 ° C. or higher. Based on the knowledge that, if separated, industrially sufficient distillation separation is possible, it is preferably an active aromatic hydroxy compound, and the standard boiling point of the lowest boiling compound is an inactive aromatic hydroxy compound.
  • the standard boiling point is preferably selected to be 10 ° C. or higher with respect to the highest boiling point compound.
  • the temperature is preferably 20 ° C. or higher, and as described above, is selected in consideration of the difference in standard boiling point from the isocyanate to be produced.
  • the active aromatic hydroxy compound is selected such that the active aromatic hydroxy compound has a normal boiling point of 10 ° C. or more higher than that of the isocyanate to be produced.
  • an aromatic hydroxy compound having a standard boiling point higher than that of isocyanate an active aromatic hydroxy compound having a standard boiling point of 10 ° C. or higher than isocyanate is selected, and an aromatic hydroxy compound having a standard boiling point lower than isocyanate is selected.
  • an active aromatic hydroxy compound having a normal boiling point of 10 ° C. or more lower than that of isocyanate is selected.
  • Step (E) A step of recycling and using the urea recovered in step (D) to step (A).
  • Step (E) is a step of recycling the urea recovered in step (D) described above to step (A). Recycling is a preferable method because the amount of urea used can be reduced.
  • the mixture recovered in the step (D) may be recycled to the step (A) as it is, or only urea may be recycled. If necessary, the components to be recycled are separated or added and recycled to step (A). Separation and addition can be performed by a known method. Urea, a compound having a carbonyl group derived from urea, a hydroxy composition, and the like are analyzed and recycled as appropriate.
  • Step (G) The following step (G) is performed to recover ammonia by-produced in step (A) and / or step (B) and / or step (R), and react with carbon dioxide to regenerate urea. Recycle to A) for use. Step (G): A step of recovering ammonia by-produced, reacting with carbon dioxide to regenerate urea, and recycling to step (A) for use.
  • ammonia discharged from the condenser in the above-described step (A), step (B) and / or step (R) is absorbed into water to form ammonia water
  • the absorption refrigerator Can be used for refrigerants, woolen oil cleaning agents, raw rubber coagulants, production of various ammonium salts, treatment of NOx generated in thermal power plants, etc., photographic emulsion production, etc.
  • the urea synthesis step (hereinafter referred to as step (G)) will be described.
  • urea As a method for producing urea by reacting ammonia and carbon dioxide, a conventionally known method can be adopted. For example, ammonia and carbon dioxide are heated to a temperature of 190 ° C. to 200 ° C. at a pressure of 20 MPa to 40 MPa. The urea is produced by reacting with a ratio of ammonia to carbon dioxide in the range of 3 to 5 in stoichiometric ratio. The urea produced by such a method may be used for the reaction in step (A).
  • the hydroxy composition refers to a composition containing at least one selected from an aromatic hydroxy composition and / or an aromatic hydroxy compound and / or an alcohol.
  • FIG. 8 is a conceptual diagram in which the route 1), which is one of the embodiments, is combined with the step (D), the step (E), the step (F), and the step (G).
  • step (A) an organic primary amine and urea are reacted to produce a compound having a ureido group.
  • the aromatic hydroxy composition mainly acts as a reaction solvent. Ammonia produced as a by-product in the reaction in the step (A) can be extracted from the reaction solution to such an extent that the ammonia concentration in the reaction solution is within the above-mentioned preferred range.
  • the reaction liquid obtained in the step (A) contains a compound having a ureido group and an aromatic hydroxy composition, and depending on the raw materials used, the composition ratio of the raw materials, the reaction conditions in the step (A), etc. However, it may be a composition for transporting and storing a compound having a ureido group in the present embodiment.
  • the compound having the ureido group and an aromatic hydroxy compound are reacted to produce an N-substituted carbamic acid-O-aryl ester.
  • Ammonia produced as a by-product in the reaction of the step (B) is extracted from the reaction solution to the above-mentioned preferable range, and the ammonia is extracted together with the ammonia extracted in the step (A) in the step (G ) Used.
  • the urea produced in the step (G) is reused as a raw material for the step (A).
  • process (D) is performed simultaneously with this process (B). That is, unreacted or excess urea is removed by distillation or sublimation. At that time, the urea is preferably distilled together with a part of the aromatic hydroxy composition to be removed and recovered as a mixture with the aromatic hydroxy composition.
  • the urea recovered in the step (D) is reused as a raw material in the step (A) by the step (E).
  • the N-substituted carbamic acid-O-aryl ester obtained in step (B) is subjected to a thermal decomposition reaction in the subsequent step (F) to produce the corresponding isocyanate and aromatic hydroxy composition.
  • the aromatic hydroxy composition separated from the isocyanate in the step (F) is reused as a raw material in the step (A).
  • FIG. 9 is a conceptual diagram in which the route 2), which is one of the present embodiments, and the step (D), the step (E), the step (F), and the step (G) are combined.
  • the route 2) is an example of a preferred embodiment when a monoarylamine is used as the organic primary amine.
  • an organic primary amine (monoarylamine) and urea are reacted to produce a compound having a ureido group.
  • the aromatic hydroxy composition mainly acts as a reaction solvent. Ammonia produced as a by-product in the reaction in the step (A) can be extracted from the reaction solution to such an extent that the ammonia concentration in the reaction solution is within the above-mentioned preferred range.
  • the reaction liquid obtained in the step (A) contains a compound having a ureido group and an aromatic hydroxy composition, and depending on the raw materials used, the composition ratio of the raw materials, the reaction conditions in the step (A), etc. However, it may be a composition for transporting and storing a compound having a ureido group in the present embodiment.
  • the compound having the ureido group and an aromatic hydroxy compound are reacted to produce N-substituted carbamic acid-O-mono (aryl ester).
  • Ammonia produced as a by-product in the reaction of the step (B) is extracted from the reaction solution to the above-mentioned preferable range, and the ammonia is extracted together with the ammonia extracted in the step (A) in the step (G ) Used.
  • the urea produced in the step (G) is reused as a raw material for the step (A).
  • process (D) is performed simultaneously with this process (B). That is, unreacted or excess urea is removed by distillation or sublimation. At that time, the urea is preferably distilled together with a part of the aromatic hydroxy composition to be removed and recovered as a mixture with the aromatic hydroxy composition.
  • the urea recovered in the step (D) is reused as a raw material in the step (A) by the step (E).
  • the N-substituted carbamic acid-O-mono (aryl ester) obtained in the step (B) is bridged with a methylene group (—CH 2 —) in the subsequent step (C), so that at least two molecules of the N-substituted carbamine are obtained.
  • An N-substituted carbamic acid-O-aryl ester in which the acid-O-mono (aryl ester) is bridged with a methylene group is produced.
  • the aromatic hydroxy composition used in the step (B) is separated from the reaction solution containing N-substituted carbamic acid-O-mono (aryl ester).
  • the N-substituted carbamic acid-O-aryl ester is preferably subjected to a thermal decomposition reaction in the step (F).
  • the N-substituted carbamic acid-O-aryl ester obtained in step (C) is subjected to a thermal decomposition reaction to produce the corresponding isocyanate and aromatic hydroxy composition.
  • the aromatic hydroxy composition separated from the isocyanate in the step (F) is reused as a raw material in the step (A).
  • FIG. 10 is a conceptual diagram in which the route 3), which is one of the embodiments, is combined with the step (D), the step (E), the step (F), and the step (G).
  • step (A) an organic primary amine and urea are reacted to produce a compound having a ureido group.
  • the reaction solvent in the step (A) an alcohol and / or an aromatic hydroxy composition is preferably used.
  • Ammonia produced as a by-product in the reaction in the step (A) can be extracted from the reaction solution to such an extent that the ammonia concentration in the reaction solution is within the above-mentioned preferred range. At that time, a part of unreacted or excess urea may be extracted as a gas phase component.
  • the reaction solution of the step (A) is the composition for transferring and storing the compound having a ureido group in the present embodiment. There can be.
  • the N-substituted carbamic acid-O—R 2 ester is produced by reacting the compound having the ureido group with an alcohol.
  • Ammonia produced as a by-product in the reaction of the step (R) is extracted from the reaction solution to the above-described preferable range, and the ammonia is extracted together with the ammonia extracted in the step (A) together with the step (G ) Used.
  • the urea produced in the step (G) is reused as a raw material for the step (A).
  • process (D) is performed simultaneously with this process (R). That is, unreacted or excess urea is removed by distillation or sublimation. At that time, the urea is preferably distilled together with a part of the hydroxy composition (alcohol and / or aromatic hydroxy composition) and removed and collected as a mixture with the hydroxy composition.
  • the urea recovered in the step (D) is reused as a raw material in the step (A) by the step (E).
  • step (R) the N-substituted carbamic acid-O—R 2 ester obtained in step (R) is reacted with the aromatic hydroxy composition in step (P) to form an N-substituted carbamic acid-O-aryl ester. Convert.
  • the alcohol derived from the N-substituted carbamic acid-O—R 2 ester by-produced by the reaction is reused in the step (A).
  • step (D) performed simultaneously with the step (R)
  • the step (D) is performed simultaneously with the step (P), and the urea in the reaction solution is removed. Can be removed.
  • the urea recovered in the step (D) is also reused as a raw material for the step (A) by the step (E).
  • the N-substituted carbamic acid-O-aryl ester obtained in step (P) is subjected to a thermal decomposition reaction in the subsequent step (F) to produce the corresponding isocyanate and aromatic hydroxy composition.
  • the aromatic hydroxy composition separated from the isocyanate in the step (F) is reused as a raw material in the step (A).
  • FIG. 11 is a conceptual diagram in which route 4), which is one of the embodiments, is combined with step (D), step (E), step (F), and step (G).
  • the route 4) is an example of a preferred embodiment when a monoarylamine is used as the organic primary amine.
  • an organic primary amine (monoarylamine) and urea are reacted to produce a compound having a ureido group.
  • an alcohol and / or an aromatic hydroxy composition is preferably used as the reaction solvent in the step (A.
  • Ammonia produced as a by-product in the reaction in the step (A) can be extracted from the reaction solution to such an extent that the ammonia concentration in the reaction solution is within the above-mentioned preferred range.
  • the reaction conditions of the step (A), the reaction solution of the step (A) is the composition for transferring and storing the compound having a ureido group in the present embodiment. There can be.
  • the compound having the ureido group and an alcohol are reacted to produce N-substituted carbamic acid-O-mono (R 2 ester).
  • Ammonia produced as a by-product in the reaction of the step (R) is extracted from the reaction solution to the above-described preferable range, and the ammonia is extracted together with the ammonia extracted in the step (A) together with the step (G ) Used.
  • the urea produced in the step (G) is reused as a raw material for the step (A).
  • process (D) is performed simultaneously with this process (R). That is, unreacted or excess urea is removed by distillation or sublimation. At that time, the urea is preferably distilled together with a part of the hydroxy composition (alcohol and / or aromatic hydroxy composition) and removed and collected as a mixture with the hydroxy composition.
  • the urea recovered in the step (D) is reused as a raw material in the step (A) by the step (E).
  • the N-substituted carbamic acid-O-mono (R 2 ester) obtained in the step (R) is reacted with the aromatic hydroxy composition in the step (P) to obtain an N-substituted carbamic acid-O—. Convert to mono (aryl ester).
  • the alcohol derived from N-substituted carbamic acid-O-mono (R 2 ester) by-produced by the reaction is reused in step (A).
  • step (D) performed simultaneously with the step (R)
  • the step (D) is performed simultaneously with the step (P)
  • the urea in the reaction solution is removed. Can be removed.
  • the urea recovered in the step (D) is also reused as a raw material for the step (A) by the step (E).
  • the N-substituted carbamic acid-O-mono (aryl ester) obtained in the step (P) is bridged with a methylene group (—CH 2 —) in the subsequent step (C), so that at least two molecules of the N-substituted carbamine are obtained.
  • N-substituted carbamic acid-O-aryl ester in which the acid-O-mono (aryl ester) is bridged with a methylene group is produced.
  • the aromatic hydroxy composition remaining in the reaction solution of the step (P) is separated from the reaction solution containing N-substituted carbamic acid-O-mono (aryl ester).
  • the N-substituted carbamic acid-O-aryl ester is preferably subjected to a thermal decomposition reaction in the step (F). Add the aromatic hydroxy composition to the ester.
  • the N-substituted carbamic acid-O-aryl ester obtained in the step (C) is subjected to a thermal decomposition reaction in the step (F) to produce a corresponding isocyanate and aromatic hydroxy composition.
  • the aromatic hydroxy composition separated from the isocyanate in the step (F) is reused as a raw material in the step (A).
  • FIG. 12 is a conceptual diagram in which the route 5), which is one of the embodiments, is combined with the step (D), the step (E), the step (F), and the step (G).
  • the route 5) is an example of a preferred embodiment when a monoarylamine is used as the organic primary amine.
  • an organic primary amine (monoarylamine) and urea are reacted to produce a compound having a ureido group.
  • an alcohol and / or an aromatic hydroxy composition is preferably used as the reaction solvent in the step (A.
  • Ammonia produced as a by-product in the reaction in the step (A) can be extracted from the reaction solution to such an extent that the ammonia concentration in the reaction solution is within the above-mentioned preferred range. At that time, a part of unreacted or excess urea may be extracted as a gas phase component.
  • the reaction conditions of the step (A) the reaction solution of the step (A) is the composition for transferring and storing the compound having a ureido group in the present embodiment. There can be.
  • the compound having the ureido group and an alcohol are reacted to produce N-substituted carbamic acid-O-mono (R 2 ester).
  • Ammonia produced as a by-product in the reaction of the step (R) is extracted from the reaction solution to the above-described preferable range, and the ammonia is extracted together with the ammonia extracted in the step (A) together with the step (G ) Used.
  • the urea produced in the step (G) is reused as a raw material for the step (A).
  • process (D) is performed simultaneously with this process (R). That is, unreacted or excess urea is removed by distillation or sublimation. At that time, the urea is preferably distilled together with a part of the hydroxy composition (alcohol and / or aromatic hydroxy composition) and removed and collected as a mixture with the hydroxy composition.
  • the urea recovered in the step (D) is reused as a raw material in the step (A) by the step (E).
  • the N-substituted carbamic acid-O-mono (R 2 ester) obtained in the step (R) is cross-linked with a methylene group (—CH 2 —) in the step (C), so that at least two molecules of the N-substituted carbamic acid-O-mono (R 2 ester) are cross-linked.
  • An N-substituted carbamic acid-O—R 2 ester in which a —substituted carbamic acid-O-mono (R 2 ester) is cross-linked with a methylene group is produced.
  • the hydroxy composition remaining in the reaction solution of the step (R) is separated from the reaction solution containing N-substituted carbamic acid-O-mono (R 2 ester).
  • the step (D) performed at the same time as the step (R) when the removal of urea is insufficient, the hydroxy composition remaining in the reaction liquid of the step (R) is separated from the semi-beneficial benefit.
  • Step (D) may be performed simultaneously to recover the urea and hydroxy composition.
  • the recovered urea and hydroxy composition is reused as a raw material for the step (A) by the step (E).
  • the obtained N-substituted carbamic acid-O—R 2 ester is subjected to a transesterification reaction in the step (P).
  • the alcohol derived from the N-substituted carbamic acid-O—R 2 ester by-produced by the reaction is reused in the step (A).
  • the N-substituted carbamic acid-O-aryl ester obtained in the step (P) is subjected to a thermal decomposition reaction in the step (F) to produce a corresponding isocyanate and aromatic hydroxy composition.
  • the aromatic hydroxy composition separated from the isocyanate in step (F) is reused as the aromatic hydroxy composition in step (P).
  • NMR analysis method JNM-A400 FT-NMR system manufactured by JEOL Ltd., Japan
  • NMR analysis method JNM-A400 FT-NMR system manufactured by JEOL Ltd., Japan
  • Preparation of 1 H and 13 C-NMR analysis samples About 0.3 g of sample solution was weighed and deuterated chloroform A solution in which about 0.7 g (US, Aldrich, 99.8%) and 0.05 g of tetramethyltin (Wako Pure Chemical Industries, Japan, Wako First Grade) as an internal standard substance were added and mixed uniformly. was used as an NMR analysis sample.
  • Quantitative analysis method Each standard substance was analyzed, and based on the prepared calibration curve, quantitative analysis of the analysis sample solution was performed.
  • Detector refractometer and PDA detector (photodiode array detector, measurement wavelength range: 200 nm to 300 nm)
  • PDA detector photodiode array detector, measurement wavelength range: 200 nm to 300 nm
  • Sample for liquid chromatography analysis About 0.1 g of the sample was weighed, about 1 g of tetrahydrofuran (made by Wako Pure Chemical Industries, Japan, dehydration) and 1,1-diethylurea (Tokyo, Japan) as an internal standard substance. A solution obtained by adding about 0.02 g (made by Kasei Co., Ltd.) and mixing uniformly was used as a sample for liquid chromatography analysis.
  • Quantitative analysis method Each standard substance was analyzed, and based on the prepared calibration curve, quantitative analysis of the analysis sample solution was performed.
  • the apparatus shown in Fig. 13 was used. In a state where the line 13 is closed, 41.84 kg of p-heptylphenol (manufactured by Schenectady, USA) and 3.10 kg of urea are mixed as an aromatic hydroxy compound in a storage tank 101 heated to 120 ° C. to obtain a mixed solution. It was. The water concentration in the mixture was about 15 ppm. The mixed solution was transferred to a stirring vessel 103 (with a baffle) heated to 120 ° C.
  • the packed tower 105 filled with the filler Helipak No. 3
  • the internal pressure was set to 26 kPa.
  • the reaction solution obtained in the step (A) was fed at about 1.5 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 35.1 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the vapor phase component was condensed by the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 via the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was analyzed by 1 H-NMR, the condensed component contained urea and p-heptylphenol.
  • the reaction liquid recovered in the storage tank 110 was 23.0 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR.
  • the reaction solution contained N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester), and N, N
  • the yield of '-hexanediyl-di (carbamic acid (p-heptylphenyl) ester) relative to hexamethylenediamine was about 97%.
  • the urea content of the reaction solution was below the lower detection limit.
  • N, N′-bis (6- (p-heptylphenoxycarbamino-hexyl) urea was not detected from the reaction solution, and the ammonia concentration in the reaction solution was 9.0 ppm.
  • the mixture recovered in the storage tank 109 was 13.5 kg.
  • the mixture contains an aromatic hydroxy compound (p-heptylphenol) and urea, the aromatic hydroxy compound (p-heptylphenol) content in the mixture is 85.4 wt%, and the urea content is 10.2 wt%. Met.
  • the apparatus shown in FIG. 17 was used.
  • a thin film distillation apparatus 602 manufactured by Shinko Environmental Solution Co., Ltd., Japan
  • the pressure in the thin film distillation apparatus was set to about 1.3 kPa.
  • the reaction liquid collected in the storage tank 110 in the step (B) was put into the storage tank 601 and supplied to the thin film distillation apparatus through the line 60 at a rate of about 1800 g / hr.
  • a liquid component was extracted from a line 62 provided at the bottom of the thin film distillation apparatus 602 and collected in a storage tank 603.
  • the liquid component recovered in the storage tank 603 was supplied again to the thin film distillation apparatus 602 via the line 63.
  • a gas component containing hexamethylene diisocyanate and p-heptylphenol was extracted from a line 61 provided at the top of the thin film distillation apparatus 602.
  • the gaseous component was introduced into the distillation column 604, and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 609 from a line 68 provided below the feed line to the distillation column 604, and further subjected to distillation separation.
  • the gas phase component was condensed by the condenser 610 via the line 69 and collected in the storage tank 612 via the gas-liquid separator 611.
  • the condensate was analyzed by 1 H-NMR and gas chromatography.
  • the condensate contained about 99 wt% hexamethylene diisocyanate.
  • the yield based on the organic amine (hexamethylenediamine) in step (A) was about 90%.
  • a mixture containing p-heptylphenol was obtained.
  • the ammonia concentration in the mixture recovered in storage tank 109 was 820 ppm.
  • 12.8 kg of p-heptylphenol and 0.578 kg of urea were added and transferred to the stirring vessel 103, and 0.92 kg of hexamethylenediamine was used, and the same method as in step (A) was performed.
  • a solution containing 6.3 wt% of 1,6-hexanediurea was obtained. The solution was used in place of the solution in step (A) and the same method as in step (B) was performed.
  • the reaction liquid recovered in the storage tank 610 contains N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester), and N, N′-hexanediyl-di (carbamic acid (hexadiene) with respect to hexamethylenediamine.
  • the yield of p-heptylphenyl) ester was about 97%.
  • Example 2 Process for producing N-substituted carbamic acid-O-aryl ester by route 1)
  • A Production of compound having ureido group The apparatus shown in Fig. 14 was used. With the line 23 closed, a liquid mixture of 1.92 kg of urea and 11.9 kg of solvent (1-butanol) was transferred from the storage tank 200 to the stirring tank 203 heated to 120 ° C. While stirring the agitation tank 203, 0.930 kg of hexamethylenediamine as an organic amine is supplied from the storage tank 201 via the line 21 to the agitation tank 103 at a rate of about 5 g / min (organic amine supply rate). did.
  • the mixture was stirred for about 1 hour.
  • the reaction solution contained 11.2 wt% of 1,1 ′-(hexane-1,6-diyl) diurea.
  • the ammonia concentration in the reaction solution was 7500 ppm.
  • the ratio of unreacted amino groups to ureido groups was 0.001.
  • 23.1 kg of p-heptylphenol was transferred from the storage tank 202 to the stirring tank 203 to form a uniform solution, and then transferred to the storage tank 204.
  • the packed tower 205 filled with the filler Helipak No. 3
  • the internal pressure was set to 10 kPa.
  • the reaction solution obtained in the step (A) was fed to the packed column 205 at a rate of about 8.2 g / min.
  • a gas component was recovered from the line 25, condensed in the condenser 206, and then recovered in the storage tank 208.
  • the recovered liquid obtained in the storage tank 208 was a mixed liquid containing 1-butanol and urea.
  • the residual liquid recovered in the storage tank 209 from the bottom of the packed column 205 via the line 26 was a mixed liquid containing 1,1 ′-(hexane-1,6-diyl) diurea and p-heptylphenol. .
  • the recovered amount of the residual liquid was about 13.5 kg.
  • the concentration of 1,1 ′-(hexane-1,6-diyl) diurea in the residual liquid is about 12.0 wt%, and the ratio of the number of p-heptylphenol to the number of ureido groups is about 2.9. there were.
  • about 9.8 kg of a mixture containing 1-butanol and urea was recovered in the storage tank 208.
  • the 1-butanol contained in the mixture was 92.5 wt%, and urea was 7.1 wt%.
  • the packed tower 210 filled with the filler Helipak No. 3
  • the internal pressure was set to 26 kPa.
  • the residual liquid recovered in the storage tank 209 in the step (D) was fed at about 3.8 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 8.95 kg.
  • the reaction solution was recovered in the storage tank 216 via the line 31 provided at the bottom of the packed tower 210.
  • a gas phase component is extracted from the line 29 provided at the top of the packed column 210, condensed in the condenser 211, and the obtained liquid phase component is recovered in the storage tank 213 through the gas-liquid separator 212 and circulated to the packed column 210. did.
  • ammonia was discharged from the line 31 as a gas component. The ammonia was absorbed in water and recovered as aqueous ammonia.
  • the reaction solution collected in the storage tank 216 was analyzed by liquid chromatography and 1 H-NMR, the reaction solution contained N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester).
  • N, N′-hexanediyl-di carbamic acid (p-heptylphenyl) ester
  • ammonia concentration in the reaction solution was 8.0 ppm.
  • the apparatus shown in FIG. 17 was used.
  • the thin film distillation apparatus 602 having a heat transfer area of 0.2 m 2 was heated to 220 ° C., and the pressure in the thin film distillation apparatus was set to about 1.3 kPa.
  • the reaction liquid recovered in the storage tank 110 in the step (B) was charged into the storage tank 601 and supplied to the thin film distillation apparatus through the line 60 at a rate of about 1500 g / hr.
  • a liquid component was extracted from a line 62 provided at the bottom of the thin film distillation apparatus 602 and collected in a storage tank 603.
  • the liquid component recovered in the storage tank 603 was supplied again to the thin film distillation apparatus 602 via the line 63.
  • a gas component containing hexamethylene diisocyanate and p-heptylphenol was extracted from a line 61 provided at the top of the thin film distillation apparatus 602.
  • the gaseous component was introduced into the distillation column 604, and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 609 from a line 68 provided below the feed line to the distillation column 604, and further subjected to distillation separation.
  • the gas phase component was condensed by the condenser 610 via the line 69 and collected in the storage tank 612 via the gas-liquid separator 611.
  • the condensate was analyzed by 1 H-NMR and gas chromatography.
  • the condensate contained about 99 wt% hexamethylene diisocyanate.
  • the yield based on the organic amine (hexamethylenediamine) was about 90%.
  • the ammonia concentration in the mixture recovered in the storage tank 109 was 550 ppm.
  • 0.962 kg of urea was added to the mixture (no solvent was added), the mixture was transferred to the stirring vessel 103, and 0.930 kg of hexamethylenediamine was used, and the same method as in step (A) was performed.
  • a solution containing 14.1 wt% of 1,6-hexanebisurea was obtained. The solution was used in place of the solution in step (A) and the same method as in step (B) was performed.
  • the reaction solution collected in the storage tank 610 contains N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester), and N, N′-hexanediyl-di (carbamic acid (hexadiene) with respect to hexamethylenediamine.
  • the yield of p-heptylphenyl) ester was about 95%.
  • the apparatus shown in FIG. 13 was used. In a state where the line 13 was closed, 13.6 kg of 1-butanol and 2.49 kg of urea were mixed as a hydroxy compound in a storage tank 101 heated to 120 ° C. to obtain a mixed solution.
  • the mixed solution was transferred to a stirring vessel 103 (with a baffle) heated to 120 ° C. While stirring the agitation tank 103, 1.07 kg of hexamethylenediamine as an organic amine is supplied from the storage tank 102 via the line 12 to the agitation tank 103 at a rate of about 20 g / min (organic amine supply rate). did.
  • the packed tower 105 filled with the filler Helipak No. 3
  • the internal pressure was set to 50 kPa.
  • the reaction solution obtained in the step (A) was fed at about 3.8 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 37.8 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the gas phase component was condensed by the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 via the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was 13.3 kg, and the condensed component was analyzed by 1 H-NMR.
  • the condensed component contained urea and 1-butanol.
  • the urea content was 9.09 wt%
  • the 1-butanol content was 89.1 wt%.
  • the reaction liquid collected in the storage tank 110 was analyzed by liquid chromatography and 1 H-NMR, the reaction liquid contained N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester). , N, N′-hexanediyl-di (carbamic acid (p-heptylphenyl) ester) was about 94% based on hexamethylenediamine. Urea in the reaction solution was not detected. The ammonia contained in the reaction solution was 8.1 ppm.
  • the apparatus shown in FIG. 17 was used.
  • the thin film distillation apparatus 602 having a heat transfer area of 0.2 m 2 was heated to 220 ° C., and the pressure in the thin film distillation apparatus was set to about 1.3 kPa.
  • the reaction liquid collected in the storage tank 110 in the step (B) was put into the storage tank 601 and supplied to the thin film distillation apparatus through the line 60 at a rate of about 1800 g / hr.
  • a liquid component was extracted from a line 62 provided at the bottom of the thin film distillation apparatus 602 and collected in a storage tank 603.
  • the liquid component recovered in the storage tank 603 was supplied again to the thin film distillation apparatus 602 via the line 63.
  • a gas component containing hexamethylene diisocyanate and p-heptylphenol was extracted from a line 61 provided at the top of the thin film distillation apparatus 602.
  • the gaseous component was introduced into the distillation column 604, and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 609 from a line 68 provided below the feed line to the distillation column 604, and further subjected to distillation separation.
  • the gas phase component was condensed by the condenser 610 via the line 69 and collected in the storage tank 612 via the gas-liquid separator 611.
  • the condensate was analyzed by 1 H-NMR and gas chromatography.
  • the condensate contained about 99 wt% hexamethylene diisocyanate.
  • the yield based on the organic amine (hexamethylenediamine) was about 90%.
  • the apparatus shown in FIG. 13 was used. With the line 13 closed, 43.5 kg of 4-tert-amylphenol as an aromatic hydroxy compound and 3.61 kg of urea were mixed in a storage tank 101 heated to 80 ° C., and the mixture was heated to 80 ° C. It was transferred to a heated stirring tank 103. While stirring the agitation tank 103, 1.12 kg of aniline was supplied from the storage tank 102 via the line 12 to the agitation tank 603 at a rate of about 10 g / min (aniline supply rate).
  • reaction solution was sampled.
  • the ratio of the number of molecules of 4-tert-amylphenol to the number of ureido groups in the reaction solution was 11.
  • the ammonia contained in the reaction solution was 3800 ppm.
  • the line 63 was opened, and the reaction solution was transferred to the storage tank 604 via the line 63.
  • the packed tower 105 filled with the filler Helipak No. 3
  • the internal pressure was set to 8 kPa.
  • the reaction solution obtained in the step (A) was fed at about 1.6 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 8.95 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the gas phase component was introduced into the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 through the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was analyzed by 1 H-NMR, the condensed component contained urea and 4-tert-amylphenol.
  • the reaction liquid recovered in the storage tank 110 was 8.72 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR. As a result, the reaction solution contained N-phenylcarbamic acid (4-tert-amylphenyl) ester and N-phenylcarbamic acid.
  • the yield of (4-tert-amylphenyl) ester relative to aniline was about 93%. Ammonia contained in the reaction solution was 5.6 ppm.
  • the apparatus shown in FIG. 15 was used.
  • the reaction liquid collected in the storage tank 110 in the step (B) was charged into the stirring tank 408.
  • the stirring tank 408 was heated to 160 ° C., the internal pressure was set to 2 kPa, and the aromatic hydroxy compound was distilled off.
  • 4-tert-amylphenol which is an aromatic hydroxy compound, was condensed in the condenser 405 via the line 44 and recovered in the storage tank 407.
  • a thin film distillation apparatus 1002 (made by Shinko Environmental Solution Co., Ltd., Japan) having a heat transfer area of 0.2 m 2 was heated to 260 ° C., and the pressure in the thin film distillation apparatus was set to about 1.5 kPa.
  • the reaction solution collected in the storage tank 404 in the step (C) was charged into the storage tank 1001 and supplied to the thin film distillation apparatus at about 1200 g / hr via the line A1.
  • the liquid component was extracted from the line A4 provided at the bottom of the thin film distillation apparatus 1002 and collected in the storage tank 1003.
  • the liquid component recovered in the storage tank 1003 was supplied again to the thin film distillation apparatus 1002 via the line A3.
  • a gas component was extracted from a line A4 provided at the upper part of the thin film distillation apparatus 1002.
  • the gaseous component was introduced into the distillation column 1004 and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 1009 from line A8 provided below the feed line to the distillation column 1004, and further subjected to distillation separation.
  • the liquid phase component was supplied to the distillation column 1014 from the line A12 provided below the feed line to the distillation column 1009, and further subjected to distillation separation.
  • a gas component was extracted from a line A13 provided at the top of the distillation column 1014, condensed in a condenser 1015, and the condensate was recovered in a storage tank 1019.
  • the condensed liquid was analyzed by 1 H-NMR, it was a solution containing about 99 wt% of 4,4′-diphenylmethane diisocyanate (MDI). The yield based on aniline was about 50%.
  • step (B) of Example 3 the ammonia content of the mixture recovered in the storage tank 109 was analyzed and found to be 1800 ppm. It was. To 14.7 kg of the mixture, 19.0 kg of 4-tert-amylphenol and 0.690 kg of urea are added and transferred to a stirring tank 603, and 0.820 kg of aniline is used to perform the same method as in step (A). I did it. A solution containing 4.5% by weight of phenylurea was obtained. The solution was used in place of the solution in step (A) and the same method as in step (B) was performed. In the reaction solution collected in the storage tank 110, the yield of N-phenylcarbamic acid (4-tert-amylphenyl) ester with respect to aniline was about 93%.
  • the apparatus shown in Fig. 13 was used. With the line 13 closed, 14.6 kg of a solvent (1-octanol (manufactured by Wako Pure Chemical Industries, Japan)) and 1.47 kg of urea are mixed in a storage tank 101 heated to 120 ° C., and the mixed solution is mixed. , And transferred to a stirring tank 103 heated to 120 ° C. (inner solution 80 L, with baffle).
  • the packed tower 105 filled with the filler Helipak No. 3
  • Helipak No. 3 was heated to 190 ° C.
  • the reaction solution obtained in the step (A) was fed at about 1.1 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 15.1 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the vapor phase component was condensed by the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 via the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was analyzed by 1 H-NMR, the condensed component contained 1-octanol and urea.
  • the reaction liquid recovered in the storage tank 110 was 8.80 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR.
  • reaction solution was found to be 3-((1-octyloxy) carbonylamidomethyl) -3,5,5-trimethylcyclohexylcarbamic acid (1-
  • the yield relative to 3-aminomethyl-3,5,5-trimethylcyclohexylamine was about 95%.
  • the ammonia concentration of the reaction solution was 5.8 ppm.
  • the apparatus shown in FIG. 16 was used. To the reaction liquid obtained in the above step, 0.5 wt% of dibutyltin dilaurate as a catalyst was added to the solution, and the solution was put into the storage tank 501.
  • the packed tower 502 packed with the filler Helipak No. 3 was heated to 260 ° C., and the internal pressure was set to 26 kPa. From the line 51 provided in the packed tower 502, the mixed solution in the storage tank 501 was fed at a rate of about 1.9 g / min. It was recovered in the storage tank 505 via the line 54 provided at the bottom of the packed tower 502.
  • the gas phase component was introduced into the condenser 503 from the line 52 provided at the top of the packed tower 502, and the obtained liquid phase component was recovered in the storage tank 504 via the gas-liquid separator 507.
  • the reaction liquid recovered in the storage tank 505 was 18.2 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR. As a result, the reaction solution was found to be 3-((p-dodecylphenyloxy) carbonylamidomethyl) -3,5,5-trimethylcyclohexylcarbamic acid (p -Dodecylphenyl) ester-containing solution, and the yield based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 89%.
  • the apparatus shown in FIG. 17 was used.
  • a thin film distillation apparatus 602 manufactured by Shinko Environmental Solution Co., Ltd., Japan
  • the pressure in the thin film distillation apparatus was set to about 1.3 kPa.
  • the reaction liquid collected in the storage tank 110 in the step (B) was charged into the storage tank 601 and supplied to the thin-film distillation apparatus through the line 60 at a rate of about 1080 g / hr.
  • a liquid component was extracted from a line 62 provided at the bottom of the thin film distillation apparatus 602 and collected in a storage tank 603.
  • the liquid component recovered in the storage tank 603 was supplied again to the thin film distillation apparatus 602 via the line 63.
  • a gas component containing isophorone diisocyanate and p-dodecylphenol was extracted from a line 61 provided at the top of the thin film distillation apparatus 602.
  • the gaseous component was introduced into the distillation column 604, and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 609 from a line 68 provided below the feed line to the distillation column 604, and further subjected to distillation separation.
  • step (B) of Example 4 the ammonia content of the mixture recovered in the storage tank 109 was analyzed and found to be 1300 ppm. It was.
  • step (A) 7.57 kg of 1-octanol and 0.70 kg of urea were added to 9.4 kg of the mixture and transferred to the stirring tank 103, and 0.87 kg of 3-aminomethyl-3,5,5-trimethylcyclohexylamine was used. The same method as in step (A) was performed. A solution containing 6.3 wt% of 3- (ureidomethyl) -3,5,5-trimethylcyclohexylurea was obtained. The solution was used in place of the solution in step (A) and the same method as in step (B) was performed.
  • the reaction liquid recovered in the storage tank 110 contains 3-((3-methylbutyloxy) carbonylamidomethyl) -3,5,5-trimethylcyclohexylcarbamic acid (3-methylbutyl) ester, and 3-
  • the yield of ((3-methylbutyloxy) carbonylamidomethyl) -3,5,5-trimethylcyclohexylcarbamic acid (3-methylbutyl) ester relative to 3-aminomethyl-3,5,5-trimethylcyclohexylamine is About 95%.
  • the apparatus shown in FIG. 13 was used. With the line 13 closed, 33.5 kg of the solvent (1-nonanol) and 3.34 kg of urea are mixed in the storage tank 101 heated to 90 ° C., and the mixture is transferred to the stirring tank 103 heated to 90 ° C. did. While stirring the agitation tank 103, 1.08 kg of aniline was supplied from the storage tank 102 via the line 12 to the agitation tank 603 at a rate of about 12 g / min.
  • the mixture was stirred for about 28 hours, and the reaction solution was sampled.
  • the reaction solution contained about 5.6 wt% of phenylurea.
  • the ammonia concentration in the reaction solution was 7900 ppm. Unreacted amino groups were not detected.
  • 25.9 kg of 2-phenylphenol was added as an aromatic hydroxy compound to prepare a mixed solution.
  • the ratio of the number of alcohols to the number of ureido groups in the mixture was 10.1.
  • the line 63 was opened, and the mixed liquid was transferred to the storage tank 604 via the line 63.
  • the packed column 105 packed with packing material Helipak No. 3
  • the internal pressure was increased.
  • the reaction solution obtained in the step (A) was fed at about 1.2 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 35.8 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the gas phase component was introduced into the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 through the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was analyzed by 1 H-NMR, the condensed component contained urea and 1-nonanol.
  • the reaction liquid recovered in the storage tank 110 was 18.9 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR. As a result, the reaction solution contained N-phenylcarbamic acid- (nonyl ester), and the yield of N-phenylcarbamic acid nonyl ester with respect to aniline was About 91%.
  • the apparatus shown in FIG. 16 was used.
  • dibutyltin dilaurate as a catalyst was mixed at 0.5 wt% with respect to the mixture, and charged into the storage tank 501.
  • a packed tower 502 filled with a filler (Helipak No. 3) and having an inner diameter of 20 mm was heated to 260 ° C., and the internal pressure was set to 26 kPa. From the line 51 provided in the packed tower 105, the reaction solution obtained in the step (A) was fed at about 1.9 g / min.
  • the reaction liquid recovered in the storage tank 505 was 26.4 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR. As a result, the reaction solution was a solution containing N-phenylcarbamic acid (2-phenylphenyl) ester, and N-phenylcarbamic acid (2- The yield of phenylphenyl) ester with respect to aniline was 89%.
  • the apparatus shown in FIG. 15 was used.
  • the reaction liquid recovered in the storage tank 505 in the step (B) was charged into the stirring tank 408.
  • the stirring vessel 408 was heated to 160 ° C., and the internal pressure was set to 1 kPa to distill 2-phenylphenol.
  • the 2-phenylphenol was condensed in the condenser 405 via the line 44 and collected in the storage tank 407.
  • a thin film distillation apparatus 1002 (made by Shinko Environmental Solution Co., Ltd., Japan) having a heat transfer area of 0.2 m 2 was heated to 260 ° C., and the pressure in the thin film distillation apparatus was set to about 1.5 kPa.
  • the reaction solution collected in the storage tank 404 in the step (C) was charged into the storage tank 1001 and supplied to the thin film distillation apparatus at about 1200 g / hr via the line A1.
  • the liquid component was extracted from the line A4 provided at the bottom of the thin film distillation apparatus 1002 and collected in the storage tank 1003.
  • the liquid component recovered in the storage tank 1003 was supplied again to the thin film distillation apparatus 1002 via the line A3.
  • a gas component was extracted from a line A4 provided at the upper part of the thin film distillation apparatus 1002.
  • the gaseous component was introduced into the distillation column 1004 and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 1009 from line A8 provided below the feed line to the distillation column 1004, and further subjected to distillation separation.
  • the liquid phase component was supplied to the distillation column 1014 from the line A12 provided below the feed line to the distillation column 1009, and further subjected to distillation separation.
  • step (A) A solution containing about 6.8 wt% phenylurea was obtained.
  • the solution was used in place of the solution in step (A) and the same method as in step (B) was performed.
  • the yield of N-phenylcarbamic acid- (nonyl ester) relative to aniline was about 91%.
  • the apparatus shown in FIG. 13 was used. With the line 13 closed, 25.4 kg of the solvent (1-heptanol) and 3.50 kg of urea are mixed in the storage tank 101 heated to 90 ° C., and the mixture is transferred to the stirring tank 103 heated to 90 ° C. did. While stirring the agitation tank 103, 1.13 kg of aniline was supplied from the storage tank 102 via the line 12 to the agitation tank 603 at a rate of about 18 g / min.
  • the mixture was stirred for about 28 hours, and the reaction solution was sampled.
  • the reaction solution contained about 7.4 wt% of phenylurea.
  • the ammonia concentration in the reaction solution was 8300 ppm. Unreacted amino groups were not detected.
  • 24.2 kg of 2,4-di-tert-amylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydroxy compound was added to prepare a mixed solution.
  • the ratio of the number of alcohols to the number of ureido groups in the mixture was 9.0.
  • the line 63 was opened, and the reaction solution was transferred to the storage tank 604 via the line 63.
  • a packed tower 105 filled with a packing material Helipack No. 3 having an inner diameter of 40 mm is heated to 190 ° C., The internal pressure was 50 kPa.
  • the reaction solution obtained in the step (A) was fed at about 1.0 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 28.0 kg. It was recovered in the storage tank 110 via the line 16 provided at the bottom of the packed tower 105.
  • the vapor phase component was condensed by the condenser 106 from the line 15 provided at the uppermost part of the packed tower 105, and the obtained liquid phase component was recovered in the storage tank 109 via the gas-liquid separator 108.
  • the condensed component recovered in the storage tank 109 was analyzed by 1 H-NMR, the condensed component contained urea and 1-heptanol.
  • the reaction liquid recovered in the storage tank 110 was 13.8 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR. As a result, the reaction solution contained N-phenylcarbamic acid (1-heptyl) ester, and the yield based on aniline was about 90%.
  • the apparatus shown in FIG. 15 was used.
  • the reaction liquid collected in the storage tank 110 in the step (R) was charged into the stirring tank 408.
  • the stirring vessel 408 was heated to 160 ° C., and the internal pressure was set to 1 kPa to distill 1-heptanol.
  • 1-Heptanol was condensed by a condenser 405 via a line 44 and collected in a storage tank 407.
  • the apparatus shown in FIG. 16 was used.
  • As a catalyst 0.5 wt% of dibutyltin dilaurate was added to the mixed solution obtained in the step (C), and the mixed solution was put into the storage tank 501.
  • reaction liquid recovered in the storage tank 505 was 25.0 kg.
  • the reaction solution was analyzed by liquid chromatography and 1 H-NMR, and it was found that the reaction solution was N, N ′-(methanediyl-diphenyl) -bis (carbamic acid (2,4-di-tert-amylphenyl)). Ester).
  • a thin film distillation apparatus 1002 (made by Shinko Environmental Solution Co., Ltd., Japan) having a heat transfer area of 0.2 m 2 was heated to 260 ° C., and the pressure in the thin film distillation apparatus was set to about 1.5 kPa.
  • the reaction solution collected in the storage tank 404 in the step (C) was charged into the storage tank 1001 and supplied to the thin film distillation apparatus at about 1200 g / hr via the line A1.
  • the liquid component was extracted from the line A4 provided at the bottom of the thin film distillation apparatus 1002 and collected in the storage tank 1003.
  • the liquid component recovered in the storage tank 1003 was supplied again to the thin film distillation apparatus 1002 via the line A3.
  • a gas component was extracted from a line A4 provided at the upper part of the thin film distillation apparatus 1002.
  • the gaseous component was introduced into the distillation column 1004 and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 1009 from line A8 provided below the feed line to the distillation column 1004, and further subjected to distillation separation.
  • the liquid phase component was supplied to the distillation column 1014 from the line A12 provided below the feed line to the distillation column 1009, and further subjected to distillation separation.
  • a gas component was extracted from a line A13 provided at the top of the distillation column 1014, condensed in a condenser 1015, and the condensate was recovered in a storage tank 1019.
  • the condensed liquid was analyzed by 1 H-NMR, it was a solution containing about 99 wt% of 4,4′-diphenylmethane diisocyanate (MDI). The yield based on aniline was about 47%.
  • the ammonia content of the mixture recovered in the storage tank 109 was analyzed and found to be 900 ppm. It was.
  • 9.48 kg of 1-heptanol and 1.54 kg of urea were added and transferred to a stirring vessel 603, and 1.12 kg of aniline was used, and the same method as in step (A) was performed.
  • a solution containing about 7.4 wt% of phenylurea was obtained.
  • the solution was used in place of the solution in step (A) and the same method as in step (B) was performed.
  • the reaction solution collected in the storage tank 110 had a yield of N-phenylcarbamic acid- (heptyl ester) with respect to aniline of about 90%.
  • Example 8 to [Example 30] The same method as in Example 1 was carried out by changing the compound used and the reaction conditions.
  • Tables 2 and 3 show the compounds, reaction conditions, and results used in Step (A) of Examples 8 to 30.
  • Tables 4 and 5 show the compounds, reaction conditions, and results used in Steps (B) and (D) of Examples 8 to 30.
  • Tables 6 and 7 show the compounds, reaction conditions, and results used in Step (F) of Examples 8 to 30.
  • step (F) “FIG. 17” and “FIG. 18” are described in the “device diagram” column, but “FIG. 17” uses the device shown in FIG. This shows that the process was performed in the same manner as in step (F) of Example 1.
  • FIG. 17 uses the device shown in FIG.
  • HDA represents hexamethylenediamine.
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine.
  • TDA 2,4-toluenediamine.
  • MDA 4,4′-methylenedianiline.
  • H-MDA 4,4′-methylenedi (cyclohexylamine).
  • Example 31] to [Example 42] The same method as in Example 2 was performed while changing the compound to be used and the reaction conditions.
  • Table 10 shows the compounds used in step (A) of each of Examples 31 to 42, reaction conditions, and results.
  • Table 11 shows the operating conditions and results of step (D) in Examples 21 to 32.
  • Table 12 shows the compounds, reaction conditions and results used in Step (B) and Step (F) of Examples 26 to 37.
  • FIG. 17 and “FIG. 18” are described in the “device diagram” column, but “FIG. 17” shows the step (F) as shown in FIG. Is used to indicate that the process was performed in the same manner as in step (F) of Example 1.
  • FIG. 18 shows that the step (F) was performed in the same manner as the step (F) of Example 4 by using an apparatus as shown in FIG.
  • Table 13 shows the compounds, reaction conditions, and results used in Step (E) of Examples 31 to 42.
  • Example 43] to [Example 49] The same method as in Example 3 was carried out by changing the compound used and the reaction conditions.
  • Table 14 shows the compounds, reaction conditions, and results used in Step (A) of Examples 43 to 49.
  • Table 15 shows the compounds, reaction conditions, and results used in Steps (B) and (D) of Examples 43 to 49.
  • step (F) of Table 15 “FIG. 17” and “FIG. 18” are described in the “device diagram” column, but “FIG. Is used in the same manner as in step (F) of Example 1.
  • FIG. 18 shows that the step (F) was performed in the same manner as the step (F) of Example 4 by using an apparatus as shown in FIG.
  • Table 16 shows the compounds, reaction conditions, and results used in Step (E) of Examples 43 to 49.
  • Example 50 to [Example 52] The same method as in Example 4 was carried out by changing the compound used and the reaction conditions.
  • Table 17 shows the compounds used in Step (A) of each Example 50 to 52, reaction conditions, and results.
  • Table 18 shows the operating conditions and results of the steps (B) and (D) of Examples 50 to 52.
  • Table 19 shows the compounds, reaction conditions, and results used in Step (C) of Examples 50 to 52.
  • Table 20 shows the reaction conditions of the step (F) in each of Examples 50 to 52.
  • the description in the column “FIG. 18” in the “apparatus diagram” in Table 20 indicates that the apparatus as shown in FIG. 18 was used in the step (F).
  • Example 53 shows the same method as in Example 5 by changing the compound used and the reaction conditions.
  • Tables 21 and 22 show the compounds, reaction conditions, and results used in Step (A) of Examples 53 to 67.
  • Tables 23 and 24 show the operating conditions and results of the steps (R) and (D) of Examples 53 to 67.
  • Table 25 and Table 26 show the compounds, reaction conditions and results used in Step (P) and Step (F) of Examples 53 to 67.
  • step (F) of Table 25 and Table 26 there are descriptions of “FIG. 17” and “FIG. 18” in the column of “apparatus diagram”. “FIG. 17” shows the step (F) in FIG.
  • FIG. 18 shows that the step (F) was performed in the same manner as the step (F) of Example 4 by using an apparatus as shown in FIG.
  • Table 27 shows the compounds, reaction conditions, and results used in Step (E) of Examples 53 to 67.
  • Example 68] to [Example 70] The same method as in Example 6 was carried out by changing the compound used and the reaction conditions.
  • Table 28 shows the compounds, reaction conditions, and results used in Step (A) of Examples 68 to 70.
  • Table 29 shows the operating conditions and results of Step (R) and Step (D) of Examples 68 to 70.
  • Table 30 shows the compounds, reaction conditions, and results used in Step (P) of Examples 68 to 70.
  • Table 31 shows the compounds, reaction conditions and results used in Step (C) of Examples 68 to 70.
  • Table 32 shows the compounds, reaction conditions and results used in Step (F) of Examples 68 to 70. In step (F) of Table 32, “FIG. 17” and “FIG. 18” are described in the column of “device drawing”.
  • FIG. 17 shows the step (F) as shown in FIG. Is used in the same manner as in step (F) of Example 1.
  • FIG. 18 shows that the step (F) was performed in the same manner as the step (F) of Example 4 by using an apparatus as shown in FIG.
  • Example 71 to [Example 73] The same method as in Example 7 was carried out by changing the compound used and the reaction conditions.
  • Table 33 shows the compounds, reaction conditions, and results used in Step (A) of Examples 71 to 73.
  • Table 34 shows the operating conditions and results of the steps (R) and (D) of Examples 71 to 73.
  • Table 35 shows the compounds used in Step (C) of each Example 71 to 73, reaction conditions and results.
  • Table 36 shows the reaction conditions and results of Step (P) and Step (F) in Examples 71 to 73.
  • step (F) of Table 36 “FIG. 18” is described in the column of “apparatus diagram”, but “FIG. 18” uses the apparatus as shown in FIG. This shows that it was carried out in the same manner as in step (F) of Example 4.
  • Step (74-1) Production of compound having ureido group
  • the apparatus shown in FIG. 19 was used. With the line B3 closed, 2.54 kg of urea was transferred from the storage tank 1100 to the storage tank 1103. After the storage tank 1103 is heated to 150 ° C. to melt urea, 0.820 kg of hexamethylenediamine is stirred from the storage tank 1101 via the line A1 to the stirring tank 1103 while stirring the stirring tank 1103. It was supplied at a rate of 10 g / min.
  • the mixture was stirred for about 1 hour, and about 8.5 kg of water was charged into the storage tank 1103 from the storage tank 1102 to obtain a slurry-like liquid.
  • the liquid was fed to a pressure filtration device 1104 to separate and separate solid components.
  • the recovered solid component was analyzed by 1 H-NMR. As a result, the solid component contained a compound having a ureylene group.
  • About 50 kg of water at about 80 ° C. was added to the solid component, stirred to obtain a dispersion, and the dispersion was filtered to obtain a filtrate. The filtrate was cooled, and the precipitated solid component was separated and collected by filtration.
  • the recovered solid component was heated to about 100 ° C.
  • the solid was 1,1 ′-(hexane-1,6-diyl) diurea.
  • the above operation was repeated 10 times to obtain about 1270 g of 1,1 ′-(hexane-1,6-diyl) diurea.
  • the apparatus shown in FIG. 20 was used. 1,1 ′-(Hexane-1,6-diyl) diurea obtained in step (74-1) and 25.9 kg of 4- (1,1,3,3-tetomethylbutyl) phenol were mixed to obtain a raw material solution And put into the storage tank 1201.
  • the packed tower 1202 filled with the filler (Helipak No. 3) was heated to 240 ° C., and the internal pressure was set to 26 kPa. From the line C1 provided in the packed tower 1202, the raw material solution was fed at about 3.5 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 23.2 kg.
  • the reaction solution was recovered in the storage tank 1205 via the line C4 provided at the bottom of the packed tower 1202.
  • the gas phase component was extracted from the line C2 provided at the top of the packed column 1202 and condensed in the condenser 1203.
  • the obtained liquid phase component was refluxed to the packed column 1202 via the gas-liquid separator 1204.
  • ammonia was recovered from the gas-liquid separator 1204 as a gas component.
  • reaction solution collected in the storage tank 1205 was analyzed by liquid chromatography and 1 H-NMR, the reaction solution was found to be N, N′-hexanediyl-di (carbamic acid (4- (1,1,3,3 N, N'-hexanediyl-di (carbamic acid (4- (1,1,3,3-tetramethylbutyl) phenyl) ester), hexamethylenediamine
  • the yield with respect to was 86%.
  • the apparatus shown in FIG. 17 was used.
  • the thin film distillation apparatus 602 having a heat transfer area of 0.2 m 2 was heated to 220 ° C., and the pressure in the thin film distillation apparatus was set to about 1.3 kPa.
  • the reaction liquid collected in the storage tank 110 in the step (B) was put into the storage tank 601 and supplied to the thin film distillation apparatus through the line 60 at a rate of about 1800 g / hr.
  • a liquid component was extracted from a line 62 provided at the bottom of the thin film distillation apparatus 602 and collected in a storage tank 603.
  • the liquid component recovered in the storage tank 603 was supplied again to the thin film distillation apparatus 602 via the line 63.
  • a gas component containing hexamethylene diisocyanate and p-heptylphenol was extracted from a line 61 provided at the top of the thin film distillation apparatus 602.
  • the gaseous component was introduced into the distillation column 604, and the low boiling component was distilled and separated.
  • the liquid phase component was supplied to the distillation column 609 from a line 68 provided below the feed line to the distillation column 604, and further subjected to distillation separation.
  • the gas phase component was condensed by the condenser 610 via the line 69 and collected in the storage tank 612 via the gas-liquid separator 611.
  • the condensate was analyzed by 1 H-NMR and gas chromatography.
  • the condensate contained about 99 wt% hexamethylene diisocyanate.
  • the yield based on hexamethylenediamine was about 80%.
  • Step (75-1) Production of compound having ureido group
  • the same method as in Step (74-1) of Example 74 was carried out, except that 3.41 kg of urea and 1.11 kg of hexamethylenediamine were used.
  • the same operation was repeated 10 times, and the obtained 1,1 ′-(hexane-1,6-diyl) diurea was mixed with about 25.6 kg of 4-ethoxyphenol to obtain a uniform solution.
  • the solution was a solution containing 6.3 wt% of 1,1 ′-(hexane-1,6-diyl) diurea and 7.7 wt% of urea.
  • the apparatus shown in FIG. 20 was used.
  • the solution obtained in the step (75-1) was put into the storage tank 401.
  • the packed tower 1202 was heated to 240 ° C., and the internal pressure was set to 26 kPa.
  • From the line 41 provided in the packed column 1202, the solution obtained in the step (75-1) was fed at about 3.7 g / min. Since the initial reaction was unsteady, the sample was discarded.
  • the reaction solution fed after reaching a steady state was about 24.3 kg.
  • the reaction solution was recovered in the storage tank 1205 via the line 44 provided at the bottom of the packed tower 1202.
  • the gas phase component is extracted from the line C2 provided at the top of the packed column 1202, condensed in the condenser 1203 maintained at about 85 ° C., and the resulting liquid phase component is passed through the gas-liquid separator 1204 to the storage tank 1207. It was collected. On the other hand, ammonia was recovered from the gas-liquid separator 1204 as a gas component.
  • the reaction liquid collected in the storage tank 1205 was analyzed by liquid chromatography and 1 H-NMR, the reaction liquid contained N, N′-hexanediyl-di (carbamic acid (4-ethoxyphenyl) ester).
  • N, N′-hexanediyl-di carbamic acid (4-ethoxyphenyl) ester
  • the solution recovered in the storage tank 1207 was 16.1 kg.
  • the solution was analyzed by 1 H-NMR, it contained 11.6 wt% of urea.
  • Step (76-1) Production of compound having ureido group Except that 3.33 kg of urea was used and 1.18 kg of 3-aminomethyl-3,5,5-trimethylcyclohexylamine was used instead of hexamethylenediamine. The same method as in step (74-1) of Example 74 was performed. The same operation was repeated 10 times to obtain 1.53 kg of a solid. Analysis by 1 H-NMR revealed that the solid was 3- (ureidomethyl) -3,5,5-trimethylcyclohexylurea.
  • the solid material obtained in Step (76-1) and 21.3 kg of p-heptylphenol were mixed to form a raw material solution, and charged into the storage tank 401.
  • the same method as in Example (56-2) was performed except that the raw material solution was fed at about 2.8 g / min.
  • the reaction solution fed after reaching a steady state was about 19.7 kg.
  • the reaction solution collected in the storage tank 405 was analyzed by liquid chromatography and 1 H-NMR, the reaction solution was found to be 3-((p-heptylphenoxy) carbonylamino-methyl) -3,5,5-trimethylcyclohexyl.

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Abstract

L'invention porte sur un procédé pour la préparation d'un ester O-arylique d'acide carbamique N-substitué issu d'un composé contenant uréido. Le procédé comprend une étape de préparation d'un ester O-arylique d'acide carbamique N-substitué à partir à la fois d'un composé contenant uréido et d'une composition de composé hydroxyle contenant au moins un composé hydroxyle soit par estérification soit à la fois par estérification et transestérification.
PCT/JP2009/005013 2009-08-21 2009-09-29 Procédé pour la préparation d'ester d'acide carbamique n-substitué et procédé pour la préparation d'isocyanate à l'aide de l'ester d'acide carbamique n-substitué WO2011021258A1 (fr)

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US13/001,238 US8884047B2 (en) 2009-08-21 2009-09-29 N-substituted carbamic acid ester production method and isocyanate production method using the N-substituted carbamic acid ester
CN200980124092.1A CN102105439B (zh) 2009-08-21 2009-09-29 N-取代氨基甲酸酯的制造方法和使用该n-取代氨基甲酸酯的异氰酸酯的制造方法
RU2010152832/04A RU2528423C2 (ru) 2009-08-21 2009-09-29 Способ получения сложного эфира n-замещенной карбаминовой кислоты и способ получения изоцианата с использованием сложного эфира n-замещенной карбаминовой кислоты
CA2724634A CA2724634C (fr) 2009-08-21 2009-09-29 Methode de production d'ester d'acide carbamique n-substitue et methode de production d'isocyanate au moyen dudit ester
ES09845052.1T ES2609025T3 (es) 2009-08-21 2009-09-29 Procedimiento para la preparación de éster de ácido carbámico sustituido en el N y procedimiento para la preparación de isocianato utilizando el éster de ácido carbámico sustituido en el N
KR1020107028732A KR101332485B1 (ko) 2009-08-21 2009-09-29 Ｎ-치환 카르밤산 에스테르의 제조 방법 및 상기 ｎ-치환 카르밤산 에스테르를 사용하는 이소시아네이트의 제조 방법
JP2010539966A JP5067906B2 (ja) 2009-08-21 2009-09-29 Ｎ−置換カルバミン酸エステルの製造方法および該ｎ−置換カルバミン酸エステルを使用するイソシアネートの製造方法
EP09845052.1A EP2322504B9 (fr) 2009-08-21 2009-09-29 Procédé pour la préparation d'ester d'acide carbamique n-substitué et procédé pour la préparation d'isocyanate à l'aide de l'ester d'acide carbamique n-substitué
BRPI0919143-7A BRPI0919143B1 (pt) 2009-08-21 2009-09-29 Método para produzir pelo menos um o-aril éster de ácido carbâmico n-substituído, e, composição para transferência e armazenamento de um composto tendo um grupo ureído
US14/490,027 US9249090B2 (en) 2009-08-21 2014-09-18 N-substituted carbamic acid ester production method and isocyanate production method using the N-substituted carbamic acid ester

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PCT/JP2009/005013 WO2011021258A1 (fr) 2009-08-21 2009-09-29 Procédé pour la préparation d'ester d'acide carbamique n-substitué et procédé pour la préparation d'isocyanate à l'aide de l'ester d'acide carbamique n-substitué

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JP2012136481A (ja) * 2010-12-27 2012-07-19 Asahi Kasei Chemicals Corp ウレイド基を有する化合物の製造方法
JP2013151453A (ja) * 2012-01-25 2013-08-08 Asahi Kasei Chemicals Corp Ｎ−置換カルバミン酸エステルの製造方法
WO2014157636A1 (fr) * 2013-03-29 2014-10-02 旭化成ケミカルズ株式会社 Procédé de production d'isocyanate
US10308601B2 (en) 2013-03-05 2019-06-04 Asahi Kasei Chemicals Corporation Isothiocyanate production method, composition for transporting and storing N-substituted O-substituted thiocarbamate, and isothiocyanate composition
WO2023106377A1 (fr) 2021-12-08 2023-06-15 旭化成株式会社 Procédé de production d'un composé isocyanate bloqué et procédé de production d'un composé isocyanate

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JPWO2023080257A1 (fr) * 2021-11-08 2023-05-11
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JP2013151453A (ja) * 2012-01-25 2013-08-08 Asahi Kasei Chemicals Corp Ｎ−置換カルバミン酸エステルの製造方法
US10308601B2 (en) 2013-03-05 2019-06-04 Asahi Kasei Chemicals Corporation Isothiocyanate production method, composition for transporting and storing N-substituted O-substituted thiocarbamate, and isothiocyanate composition
US11046645B2 (en) 2013-03-05 2021-06-29 Asahi Kasei Chemicals Corporation Isothiocyanate production method, composition for transporting and storing N-substituted O-substituted thiocarbamate, and isothiocyanate composition
WO2014157636A1 (fr) * 2013-03-29 2014-10-02 旭化成ケミカルズ株式会社 Procédé de production d'isocyanate
JP6055084B2 (ja) * 2013-03-29 2016-12-27 旭化成株式会社 イソシアネートの製造方法
US9714215B2 (en) 2013-03-29 2017-07-25 Asahi Kasei Chemicals Corporation Method for producing isocyanate
KR101773830B1 (ko) 2013-03-29 2017-09-04 아사히 가세이 가부시키가이샤 이소시아네이트의 제조 방법
WO2023106377A1 (fr) 2021-12-08 2023-06-15 旭化成株式会社 Procédé de production d'un composé isocyanate bloqué et procédé de production d'un composé isocyanate

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TW201107279A (en) 2011-03-01
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US9249090B2 (en) 2016-02-02
BRPI0919143A2 (pt) 2016-11-01
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JP5043191B2 (ja) 2012-10-10
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CN103588680B (zh) 2016-08-10
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KR20110042155A (ko) 2011-04-25

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